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Modifications in Lignin and Accumulation of Phenolic THE JOURNAL OF BIOLOGICAL CHEMISTRY Vol. 275, No. 47, Issue of November 24, pp. 36899–36909, 2000 Printed in U.S.A. Modifications in Lignin and Accumulation of Phenolic Glucosides in Poplar Xylem upon Down-regulation of Caffeoyl-Coenzyme A O-Methyltransferase, an Enzyme Involved in Lignin Biosynthesis* Received for publication, August 1, 2000 Published, JBC Papers in Press, August 8, 2000, DOI 10.1074/jbc.M006415200 Hugo Meyermans,a Kris Morreel,a,b Catherine Lapierre,c Brigitte Pollet,c Andre´ De Bruyn,d Roger Busson,e Piet Herdewijn,e Bart Devreese,f,g Jozef Van Beeumen,f Jane M. Marita,h,i John Ralph,h,i Cuiying Chen,a Bart Burggraeve,a Marc Van Montagu,a Eric Messens,a and Wout Boerjana,j From the aVakgroep Moleculaire Genetica & Departement Plantengenetica, Vlaams Interuniversitair Instituut voor Biotechnologie, Universiteit Gent, B-9000 Gent, Belgium, cLaboratoire de Chimie Biologique, Institut National Agronomique Paris-Grignon, F-78850 Thiverval-Grignon, France, dVakgroep Organische Scheikunde, Universiteit Gent, B-9000 Gent, Belgium, eLaboratorium Medicinale Scheikunde, Katholieke Universiteit Leuven, B-3000 Leuven, Belgium, fVakgroep Biochemie, Fysiologie en Microbiologie, Universiteit Gent, B-9000 Gent, Belgium, and hU.S. Dairy Forage Research Center, U.S. Department of Agriculture-Agricultural Research Service, Madison, Wisconsin 53706-1108 Caffeoyl-coenzyme A O-methyltransferase (CCoAOMT) Lignin is, second to cellulose, the most abundant organic methylates, in vitro, caffeoyl-CoA and 5-hydroxyferuloyl- compound in the terrestrial biosphere. In different tree species, CoA, two possible precursors in monolignol biosynthesis in lignin content varies between 15 and 36% of the dry weight of vivo. To clarify the in vivo role of CCoAOMT in lignin bio- wood (1). Lignin is a major constituent of cell walls of fibers and synthesis, transgenic poplars with 10% residual CCoAOMT tracheary elements and provides these cells rigidity for struc- protein levels in the stem xylem were generated. Upon anal- tural support and impermeability for water transport. For the ysis of the xylem, the affected transgenic lines had a 12% production of high-quality paper, lignin is considered as a neg- reduced Klason lignin content, an 11% increased syringyl/ ative factor because it must be extracted from the cellulose guaiacyl ratio in the noncondensed lignin fraction, and an fraction by energy-requiring and polluting methods. For this increase in lignin-attached p-hydroxybenzoate but other- reason, there is considerable interest in modifying lignin by wise a lignin composition similar to that of wild type. Stem genetic engineering to improve its extractability from wood xylem of the CCoAOMT-down-regulated lines had a pink- (2–5). red coloration, which coincided with an enhanced fluores- Lignin monomer biosynthesis starts with the deamination of cence of mature vessel cell walls. The reduced production 3 phenylalanine to produce cinnamic acid (Fig. 1). Further enzy- of CCoAOMT caused an accumulation of O -␤-D-glucopyr- 4 matic reactions include the hydroxylation of the aromatic ring, anosyl-caffeic acid, O -␤-D-glucopyranosyl-vanillic acid, 4 and O -␤-D-glucopyranosyl-sinapic acid (GSA), as authenti- the methylation of selected phenolic hydroxyl groups, the acti- cated by 1H NMR. Feeding experiments showed that O3-␤- vation of the cinnamic acids to cinnamoyl-CoA esters, and the D-glucopyranosyl-caffeic acid and GSA are storage or detox- reduction of these esters to cinnamaldehydes and cinnamyl ification products of caffeic and sinapic acid, respectively. alcohols. The precise order in which these reactions occur is not The observation that down-regulation of CCoAOMT de- yet fully resolved. In dicotyledonous plants, lignin is composed creases lignin amount whereas GSA accumulates to 10% of mainly of guaiacyl (G)1 and syringyl (S) units that are mono- soluble phenolics indicates that endogenously produced si- methoxylated (C-3) and dimethoxylated (C-3, C-5) and derived napic acid is not a major precursor in syringyl lignin bio- from coniferyl alcohol and sinapyl alcohol, respectively. The synthesis. Our in vivo results support the recently obtained lignin monomers are transported to the cell wall and are sub- in vitro enzymatic data that suggest that the route from sequently polymerized, resulting in the deposition of a cross- caffeic acid to sinapic acid is not used for lignin linked polymer. Although most of the lignin biosynthesis en- biosynthesis. zymes have been characterized at the molecular level, their precise role in determining lignin amount and composition still * This work was supported by Flemish government Geconcerteerde needs to be clarified. Onderzoeksacties Grant 12052293, Fund for Scientific Research Based on in vitro data, it has been generally accepted that Flanders Grants FWO 1.5.515.98N and G.0040.00, and European the methylation reactions in lignin biosynthesis occur exclu- Union Grant FAIR-PL95424. The costs of publication of this article sively at the cinnamic acid level and that they are catalyzed by were defrayed in part by the payment of page charges. This article must a bispecific caffeic acid/5-hydroxyferulic acid O-methyltrans- therefore be hereby marked “advertisement” in accordance with 18 U.S.C. Section 1734 solely to indicate this fact. ferase (COMT) (1). However, the analysis of transgenic tobacco b Recipient of a predoctoral fellowship from Vlaams Instituut voor de and poplar with suppressed COMT activity has shown that Bevordering van het Wetenschappelijk-Technologisch Onderzoek in de Industrie. g Postdoctoral fellow of the Fund for Scientific Research (Flanders). 1 The abbreviations used are: G, guaiacyl; 4CL, 4-coumaric acid:CoA i Supported by the U.S. Department of Agriculture-Agricultural Re- ligase; CaMV, cauliflower mosaic virus; CCoAOMT, caffeoyl-CoA O- search Service and in part through U.S. Department of Agriculture- methyltransferase; COMT, caffeic acid/5-hydroxyferulic acid O-methyl- National Resources Inventory Grant 99-2351 (Improved Utilization of transferase; AldOMT, 5-hydroxyconiferaldehyde O-methyltransferase; Wood and Wood Fiber Section). GCA, O3-␤-D-glucopyranosyl-caffeic acid; GSA, O4-␤-D-glucopyranosyl- j To whom correspondence should be addressed: Dept. Plantenge- sinapic acid; GVA, O4-␤-D-glucopyranosyl-vanillic acid; HPLC, high netica, Vlaams Interuniversitair Instituut voor Biotechnologie, Univer- pressure liquid chromatography; MS, mass spectrometry; MS/MS, tan- siteit Gent, K. L. Ledeganckstraat 35, B-9000 Gent, Belgium. Tel.: dem mass spectrometry; NOE, nuclear Overhauser effect; S, syringyl; 32-9-2645202; Fax: 32-9-2645349; [email protected]. bp, base pair. This paper is available on line at http://www.jbc.org 36899 36900 Accumulation of Phenolic Glucosides FIG.1.Biosynthetic pathway for cinnamyl alcohols and production of side product phenolics. Enzymatic reactions involved in the cinnamyl alcohol biosynthesis in poplar are indicated in black. The formation of sinapoyl-CoA and its conversion to sinapaldehyde are indicated in blue; the relevance of these conversions in monolignol biosynthesis is uncertain, as mentioned above. Conversions leading to the synthesis of side product phenolics are indicated in red and are markedly up-regulated when CCoAOMT expression is reduced. The reduced flux from caffeoyl-CoA to feruloyl-CoA, caused by the down-regulated CCoAOMT expression causes an elevated production of caffeic acid that is detoxified to GCA. GVA synthesis is probably up-regulated because of an increased availability of caffeic acid (48). Caffeic acid can be converted to sinapic acid by the sequential activity of COMT/AldOMT, ferulic acid 5-hydroxylase (F5H)/coniferyl aldehyde 5-hydroxylase (CAld5H), and COMT/AldOMT. Because of the lack of 4CL activity toward sinapic acid, it cannot take part in syringyl biosynthesis, and it is detoxified and stored as GSA. p-Hydroxybenzoic acid formation can be mediated by a ␤-oxidation mechanism (conversion 1) (47) or, more probably, by an NAD-dependent p-hydroxybenzaldehyde dehydrogenase (conversion 2) (52) acting on p-coumaric acid. The formation of sinapyl alcohol from coniferyl alcohol remains ambiguous (5, 13, 14, 17, 27). PAL, phenylalanine ammonia-lyase; C4H, cinnamic acid 4-hydroxylase; C3H, coumaric acid 3-hydroxylase; CCoA3H, coumaroyl-CoA 3-hydroxylase; CCR, cinnamoyl-CoA reductase; CAD, cinnamyl alcohol dehydrogenase. Accumulation of Phenolic Glucosides 36901 COMT is mainly or exclusively implicated in the biosynthesis CaMV terminator sequence, kindly provided by L. Jouanin (INRA Ver- of S monomers (6–9). Later, it was shown that the methylation sailles, France). Subsequently, the KpnI/XbaI P70-CCoAOMT fragment of the lignin precursors could also occur at the level of the was cloned into the KpnI/XbaI sites of pBIBHYG, resulting in vector p5Ј-asCCoAOMT. cinnamoyl-CoA esters by caffeoyl-CoA-3-O-methyltransferase (10), and it was proposed that CCoAOMT was predominantly Construction of an Internal Antisense Construct involved in the biosynthesis of G units. Transgenic tobacco A 571-bp HindIII/BamHI CCoAOMT fragment was generated by plants down-regulated for CCoAOMT, however, had a reduced digesting pccoaomt-1b. This fragment was cloned into the HindIII/ lignin amount, indicating that CCoAOMT regulates both G and BamHI-digested vector OMTmutpBSrev, kindly provided by U. Matern S unit production (11). Subsequently, in vitro activity assays (Institute of Pharmaceutical Biology, Marburg, Germany), resulting in have shown that
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