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Title: Lignin biosynthesis: old roads revisited and new roads explored

Journal Article · · Open Biology
ORCiD logo [1];  [2]
  1. Texas A & M Univ., College Station, TX (United States); Univ. of North Texas, Denton, TX (United States); OSTI
  2. Univ. of North Texas, Denton, TX (United States)

Lignin is a major component of secondarily thickened plant cell walls and is considered to be the second most abundant biopolymer on the planet. At one point believed to be the product of a highly controlled polymerization procedure involving just three potential monomeric components (monolignols), it is becoming increasingly clear that the composition of lignin is quite flexible. Furthermore, the biosynthetic pathways to the major monolignols also appear to exhibit flexibility, particularly as regards the early reactions leading to the formation of caffeic acid from coumaric acid. The operation of parallel pathways to caffeic acid occurring at the level of shikimate esters or free acids may help provide robustness to the pathway under different physiological conditions. Several features of the pathway also appear to link monolignol biosynthesis to both generation and detoxification of hydrogen peroxide, one of the oxidants responsible for creating monolignol radicals for polymerization in the apoplast. Monolignol transport to the apoplast is not well understood. It may involve passive diffusion, although this may be targeted to sites of lignin initiation/polymerization by ordered complexes of both biosynthetic enzymes on the cytosolic side of the plasma membrane and structural anchoring of proteins for monolignol oxidation and polymerization on the apoplastic side. We present several hypothetical models to illustrate these ideas and stimulate further research. These are based primarily on studies in model systems, which may or may not reflect the major lignification process in forest trees.

Research Organization:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Bioenergy Innovation (CBI)
Sponsoring Organization:
National Science Foundation (NSF); USDOE Office of Science (SC), Biological and Environmental Research (BER)
OSTI ID:
1903900
Journal Information:
Open Biology, Journal Name: Open Biology Journal Issue: 12 Vol. 9; ISSN 2046-2441
Publisher:
The Royal SocietyCopyright Statement
Country of Publication:
United States
Language:
English

References (198)

Lignification: are Lignins Biosynthesized via simple Combinatorial Chemistry or via Proteinaceous Control and Template Replication? book July 2008
The Peroxidase Gene Family in Plants: A Phylogenetic Overview journal October 2003
The role of UDP-glucose:hydroxycinnamate glucosyltransferases in phenylpropanoid metabolism and the response to UV-B radiation in Arabidopsis thaliana journal June 2008
The laccase multigene family in Arabidopsis thaliana: towards addressing the mystery of their gene function(s) journal November 2010
Hydrogen peroxide permeability of plasma membrane aquaporins of Arabidopsis thaliana journal March 2011
Early lignin pathway enzymes and routes to chlorogenic acid in switchgrass (Panicum virgatum L.) journal November 2013
Transfer RNA-derived small RNAs in plants journal November 2017
Lignin-ferulate cross-links in grasses: active incorporation of ferulate polysaccharide esters into ryegrass lignins journal September 1995
Transfer RNA-derived fragments target and regulate ribosome-associated aminoacyl-transfer RNA synthetases journal July 2018
The binding versatility of plant acyl-CoA-binding proteins and their significance in lipid metabolism journal September 2016
Membrane transport of hydrogen peroxide journal August 2006
Lignin primary structures and dirigent sites journal August 2005
Development and commercialization of reduced lignin alfalfa journal April 2019
The transport of monomers during lignification in plants: anything goes but how? journal April 2019
Lignin polymerization: how do plants manage the chemistry so well? journal April 2019
The Casparian strip—one ring to bring cell biology to lignification? journal April 2019
Lignin structure and its engineering journal April 2019
AtABCG29 Is a Monolignol Transporter Involved in Lignin Biosynthesis journal July 2012
The regulatory role of shikimate in plant phenylalanine metabolism journal February 2019
Metabolon formation and metabolic channeling in the biosynthesis of plant natural products journal June 2005
Reactive oxygen species in cell wall metabolism and development in plants journal April 2015
Flavonoid transport mechanisms: how to go, and with whom journal September 2015
The biosynthesis of monolignols: a “metabolic grid”, or independent pathways to guaiacyl and syringyl units? journal August 2001
Dirigent proteins and dirigent sites in lignifying tissues journal July 2001
Rewriting the lignin roadmap journal June 2002
Structural Characterization of Lignin from Maize ( Zea mays L.) Fibers: Evidence for Diferuloylputrescine Incorporated into the Lignin Polymer in Maize Kernels journal April 2018
Role of bifunctional ammonia-lyase in grass cell wall biosynthesis journal May 2016
Whole plant cell wall characterization using solution-state 2D NMR journal August 2012
Completion of the cytosolic post-chorismate phenylalanine biosynthetic pathway in plants journal January 2019
4-Coumarate 3-hydroxylase in the lignin biosynthesis pathway is a cytosolic ascorbate peroxidase journal April 2019
The scaffold proteins of lignin biosynthetic cytochrome P450 enzymes journal April 2018
OsCAldOMT1 is a bifunctional O-methyltransferase involved in the biosynthesis of tricin-lignins in rice cell walls journal August 2019
The Arabidopsis REF8 gene encodes the 3-hydroxylase of phenylpropanoid metabolism journal April 2002
Cinnamoyl-CoA reductase, a key enzyme in lignin biosynthesis, is an effector of small GTPase Rac in defense signaling in rice journal December 2005
Exploring lignification in conifers by silencing hydroxycinnamoyl-CoA:shikimate hydroxycinnamoyltransferase in Pinus radiata journal July 2007
ATP-binding cassette-like transporters are involved in the transport of lignin precursors across plasma and vacuolar membranes journal December 2010
Membrane protein complexes catalyze both 4- and 3-hydroxylation of cinnamic acid derivatives in monolignol biosynthesis journal December 2011
A polymer of caffeyl alcohol in plant seeds journal January 2012
Dirigent domain-containing protein is part of the machinery required for formation of the lignin-based Casparian strip in the root journal August 2013
Loss of function of cinnamyl alcohol dehydrogenase 1 leads to unconventional lignin and a temperature-sensitive growth defect in Medicago truncatula journal July 2013
Lignification of plant cell walls: Impact of genetic manipulation journal October 1998
CYP98A3 from Arabidopsis thaliana Is a 3′-Hydroxylase of Phenolic Esters, a Missing Link in the Phenylpropanoid Pathway journal June 2001
Thermodynamic insights into an interaction between ACYL-CoA–BINDING PROTEIN2 and LYSOPHOSPHOLIPASE2 in Arabidopsis journal February 2019
The cell biology of lignification in higher plants journal April 2015
Lignin metabolism has a central role in the resistance of cotton to the wilt fungus Verticillium dahliae as revealed by RNA-Seq-dependent transcriptional analysis and histochemistry journal August 2011
Dirigent proteins in plants: modulating cell wall metabolism during abiotic and biotic stress exposure journal May 2017
Deciphering the Enigma of Lignification: Precursor Transport, Oxidation, and the Topochemistry of Lignin Assembly journal March 2012
Production of Reactive Oxygen Species by Plant NADPH Oxidases journal June 2006
Identification of an Arabidopsis Fatty Alcohol:Caffeoyl-Coenzyme A Acyltransferase Required for the Synthesis of Alkyl Hydroxycinnamates in Root Waxes journal July 2012
Proton-Dependent Coniferin Transport, a Common Major Transport Event in Differentiating Xylem Tissue of Woody Plants journal April 2013
Laccases Direct Lignification in the Discrete Secondary Cell Wall Domains of Protoxylem journal August 2014
Tricin, a Flavonoid Monomer in Monocot Lignification journal February 2015
Silencing CHALCONE SYNTHASE in Maize Impedes the Incorporation of Tricin into Lignin and Increases Lignin Content journal December 2016
Disrupting Flavone Synthase II Alters Lignin and Improves Biomass Digestibility journal April 2017
Silencing CAFFEOYL SHIKIMATE ESTERASE Affects Lignification and Improves Saccharification in Poplar journal September 2017
Hydroxystilbene Glucosides Are Incorporated into Norway Spruce Bark Lignin journal April 2019
Cytosolic Ascorbate Peroxidase 1 Is a Central Component of the Reactive Oxygen Gene Network of Arabidopsis journal December 2004
MATE Transporters Facilitate Vacuolar Uptake of Epicatechin 3′-O-Glucoside for Proanthocyanidin Biosynthesis inMedicago truncatulaandArabidopsis    journal August 2009
LACCASE Is Necessary and Nonredundant with PEROXIDASE for Lignin Polymerization during Vascular Development in Arabidopsis journal October 2013
Small Glycosylated Lignin Oligomers Are Stored in Arabidopsis Leaf Vacuoles journal February 2015
Stress-Induced Phenylpropanoid Metabolism. journal July 1995
Acyl-CoA-binding protein 2 binds lysophospholipase 2 and lysoPC to promote tolerance to cadmium-induced oxidative stress in transgenic Arabidopsis journal March 2010
Lack of involvement of polyphenol oxidase in ortho-hydroxylation of phenolic compounds in mung bean seedlings journal April 1982
The origin and evolution of lignin biosynthesis: Tansley review journal June 2010
Abiotic and Biotic Stresses and Changes in the Lignin Content and Composition in Plants journal April 2010
CAD 1 and CCR 2 protein complex formation in monolignol biosynthesis in Populus trichocarpa journal October 2018
An essential role of caffeoyl shikimate esterase in monolignol biosynthesis in Medicago truncatula journal June 2016
An “ideal lignin” facilitates full biomass utilization journal September 2018
Caffeoyl Shikimate Esterase (CSE) Is an Enzyme in the Lignin Biosynthetic Pathway in Arabidopsis journal August 2013
Lignin Valorization: Improving Lignin Processing in the Biorefinery journal May 2014
Monolignol Ferulate Transferase Introduces Chemically Labile Linkages into the Lignin Backbone journal April 2014
Reactive Oxygen Species in Plant Signaling journal April 2018
Altering the Cell Wall and Its Impact on Plant Disease: From Forage to Bioenergy journal August 2014
Lignin Biosynthesis journal June 2003
A horizontal gene transfer at the origin of phenylpropanoid metabolism: a key adaptation of plants to land journal January 2009
A 13C isotope labeling method for the measurement of lignin metabolic flux in Arabidopsis stems journal June 2018
Mathematical models of lignin biosynthesis journal February 2018
Integrative Analysis of Transgenic Alfalfa (Medicago sativa L.) Suggests New Metabolic Control Mechanisms for Monolignol Biosynthesis journal May 2011
tRNAs as regulators of biological processes journal June 2014
Role of lignification in plant defense journal February 2009
Lignin‐based barrier restricts pathogens to the infection site and confers resistance in plants text January 2019
Lignification: are Lignins Biosynthesized via simple Combinatorial Chemistry or via Proteinaceous Control and Template Replication? book July 2008
The Peroxidase Gene Family in Plants: A Phylogenetic Overview journal October 2003
The role of UDP-glucose:hydroxycinnamate glucosyltransferases in phenylpropanoid metabolism and the response to UV-B radiation in Arabidopsis thaliana journal June 2008
The laccase multigene family in Arabidopsis thaliana: towards addressing the mystery of their gene function(s) journal November 2010
Hydrogen peroxide permeability of plasma membrane aquaporins of Arabidopsis thaliana journal March 2011
Pea extracellular Cu/Zn-superoxide dismutase responsive to signal molecules from a fungal pathogen journal October 2006
Early lignin pathway enzymes and routes to chlorogenic acid in switchgrass (Panicum virgatum L.) journal November 2013
Lignin-ferulate cross-links in grasses: active incorporation of ferulate polysaccharide esters into ryegrass lignins journal September 1995
The biosynthesis of monolignols: a “metabolic grid”, or independent pathways to guaiacyl and syringyl units? journal August 2001
Dirigent proteins and dirigent sites in lignifying tissues journal July 2001
Rewriting the lignin roadmap journal June 2002
Transfer RNA-derived fragments target and regulate ribosome-associated aminoacyl-transfer RNA synthetases journal July 2018
The binding versatility of plant acyl-CoA-binding proteins and their significance in lipid metabolism journal September 2016
Membrane transport of hydrogen peroxide journal August 2006
A Mechanism for Localized Lignin Deposition in the Endodermis journal April 2013
Lignin primary structures and dirigent sites journal August 2005
Development and commercialization of reduced lignin alfalfa journal April 2019
The transport of monomers during lignification in plants: anything goes but how? journal April 2019
Lignin polymerization: how do plants manage the chemistry so well? journal April 2019
The Casparian strip—one ring to bring cell biology to lignification? journal April 2019
Tailor-made trees: engineering lignin for ease of processing and tomorrow’s bioeconomy journal April 2019
Lignin structure and its engineering journal April 2019
AtABCG29 Is a Monolignol Transporter Involved in Lignin Biosynthesis journal July 2012
The regulatory role of shikimate in plant phenylalanine metabolism journal February 2019
Metabolon formation and metabolic channeling in the biosynthesis of plant natural products journal June 2005
Down-regulation of hydroxycinnamoyl CoA: Shikimate hydroxycinnamoyl transferase in transgenic alfalfa affects lignification, development and forage quality journal June 2007
Pinoresinol reductase 1 impacts lignin distribution during secondary cell wall biosynthesis in Arabidopsis journal April 2015
Reactive oxygen species in cell wall metabolism and development in plants journal April 2015
Should I stay or should I go: are chlorogenic acids mobilized towards lignin biosynthesis? journal October 2019
Flavonoid transport mechanisms: how to go, and with whom journal September 2015
Structural Characterization of Lignin from Maize ( Zea mays L.) Fibers: Evidence for Diferuloylputrescine Incorporated into the Lignin Polymer in Maize Kernels journal April 2018
Disruption of Mediator rescues the stunted growth of a lignin-deficient Arabidopsis mutant journal March 2014
Lignin modification improves fermentable sugar yields for biofuel production journal June 2007
Role of bifunctional ammonia-lyase in grass cell wall biosynthesis journal May 2016
Whole plant cell wall characterization using solution-state 2D NMR journal August 2012
Completion of the cytosolic post-chorismate phenylalanine biosynthetic pathway in plants journal January 2019
4-Coumarate 3-hydroxylase in the lignin biosynthesis pathway is a cytosolic ascorbate peroxidase journal April 2019
The scaffold proteins of lignin biosynthetic cytochrome P450 enzymes journal April 2018
Membrane-bound metabolons journal April 2018
The molecular structure of plant sporopollenin journal December 2018
OsCAldOMT1 is a bifunctional O-methyltransferase involved in the biosynthesis of tricin-lignins in rice cell walls journal August 2019
The occurrence of tricin and its derivatives in plants journal January 2016
The Arabidopsis REF8 gene encodes the 3-hydroxylase of phenylpropanoid metabolism journal April 2002
Changes in secondary metabolism and deposition of an unusual lignin in the ref8 mutant of Arabidopsis journal April 2002
Cinnamoyl-CoA reductase, a key enzyme in lignin biosynthesis, is an effector of small GTPase Rac in defense signaling in rice journal December 2005
Exploring lignification in conifers by silencing hydroxycinnamoyl-CoA:shikimate hydroxycinnamoyltransferase in Pinus radiata journal July 2007
ATP-binding cassette-like transporters are involved in the transport of lignin precursors across plasma and vacuolar membranes journal December 2010
Membrane protein complexes catalyze both 4- and 3-hydroxylation of cinnamic acid derivatives in monolignol biosynthesis journal December 2011
A polymer of caffeyl alcohol in plant seeds journal January 2012
Dirigent domain-containing protein is part of the machinery required for formation of the lignin-based Casparian strip in the root journal August 2013
Ptr-miR397a is a negative regulator of laccase genes affecting lignin content in Populus trichocarpa journal June 2013
Loss of function of cinnamyl alcohol dehydrogenase 1 leads to unconventional lignin and a temperature-sensitive growth defect in Medicago truncatula journal July 2013
NMR characterization of altered lignins extracted from tobacco plants down-regulated for lignification enzymes cinnamylalcohol dehydrogenase and cinnamoyl-CoA reductase journal October 1998
CYP98A3 from Arabidopsis thaliana Is a 3′-Hydroxylase of Phenolic Esters, a Missing Link in the Phenylpropanoid Pathway journal June 2001
Thermodynamic insights into an interaction between ACYL-CoA–BINDING PROTEIN2 and LYSOPHOSPHOLIPASE2 in Arabidopsis journal February 2019
The cell biology of lignification in higher plants journal April 2015
Lignin metabolism has a central role in the resistance of cotton to the wilt fungus Verticillium dahliae as revealed by RNA-Seq-dependent transcriptional analysis and histochemistry journal August 2011
Dirigent proteins in plants: modulating cell wall metabolism during abiotic and biotic stress exposure journal May 2017
Distribution, mobility, and anchoring of lignin-related oxidative enzymes in Arabidopsis secondary cell walls journal February 2018
Phenylpropanoid Biosynthesis journal January 2010
Deciphering the Enigma of Lignification: Precursor Transport, Oxidation, and the Topochemistry of Lignin Assembly journal March 2012
Detection and Characterization of p-Coumaric Acid Hydroxylase in Mung Bean, Vigna mungo, Seedlings1 journal February 1989
Intra- and Extra-Cellular Localization of "Cytosolic" CuZn-Superoxide Dismutase in Spinach Leaf and Hypocotyl journal September 1996
Production of Reactive Oxygen Species by Plant NADPH Oxidases journal June 2006
Identification of an Arabidopsis Fatty Alcohol:Caffeoyl-Coenzyme A Acyltransferase Required for the Synthesis of Alkyl Hydroxycinnamates in Root Waxes journal July 2012
Proton-Dependent Coniferin Transport, a Common Major Transport Event in Differentiating Xylem Tissue of Woody Plants journal April 2013
Laccases Direct Lignification in the Discrete Secondary Cell Wall Domains of Protoxylem journal August 2014
Tricin, a Flavonoid Monomer in Monocot Lignification journal February 2015
Silencing CHALCONE SYNTHASE in Maize Impedes the Incorporation of Tricin into Lignin and Increases Lignin Content journal December 2016
Disrupting Flavone Synthase II Alters Lignin and Improves Biomass Digestibility journal April 2017
Hydroxystilbenes Are Monomers in Palm Fruit Endocarp Lignins journal June 2017
Silencing CAFFEOYL SHIKIMATE ESTERASE Affects Lignification and Improves Saccharification in Poplar journal September 2017
Hydroxystilbene Glucosides Are Incorporated into Norway Spruce Bark Lignin journal April 2019
Ectopic Defense Gene Expression Is Associated with Growth Defects in Medicago truncatula Lignin Pathway Mutants journal July 2019
4-Hydroxycinnamic Acid Hydroxylase and Polyphenolase Activities in Sorghum vulgare journal April 1972
Silencing of Hydroxycinnamoyl-Coenzyme A Shikimate/Quinate Hydroxycinnamoyltransferase Affects Phenylpropanoid Biosynthesis journal May 2004
Cytosolic Ascorbate Peroxidase 1 Is a Central Component of the Reactive Oxygen Gene Network of Arabidopsis journal December 2004
MATE Transporters Facilitate Vacuolar Uptake of Epicatechin 3′-O-Glucoside for Proanthocyanidin Biosynthesis inMedicago truncatulaandArabidopsis    journal August 2009
Protein–Protein and Protein–Membrane Associations in the Lignin Pathway journal November 2012
Coexistence but Independent Biosynthesis of Catechyl and Guaiacyl/Syringyl Lignin Polymers in Seed Coats journal July 2013
LACCASE Is Necessary and Nonredundant with PEROXIDASE for Lignin Polymerization during Vascular Development in Arabidopsis journal October 2013
A Genomics Approach to Deciphering Lignin Biosynthesis in Switchgrass journal November 2013
Small Glycosylated Lignin Oligomers Are Stored in Arabidopsis Leaf Vacuoles journal February 2015
Stress-Induced Phenylpropanoid Metabolism. journal July 1995
Downregulation of high-isoelectric-point extracellular superoxide dismutase mediates alterations in the metabolism of reactive oxygen species and developmental disturbances in hybrid aspen journal December 2006
Engineering traditional monolignols out of lignin by concomitant up-regulation of F5H1 and down-regulation of COMT in Arabidopsis: Concomitant F5H1 up-regulation and COMT down-regulation in Arabidopsis journal October 2010
Over-expression of F5H in COMT-deficient Arabidopsis leads to enrichment of an unusual lignin and disruption of pollen wall formation: Lignin modification leads to male sterility journal November 2010
Lack of involvement of polyphenol oxidase in ortho-hydroxylation of phenolic compounds in mung bean seedlings journal April 1982
The origin and evolution of lignin biosynthesis: Tansley review journal June 2010
Abiotic and Biotic Stresses and Changes in the Lignin Content and Composition in Plants journal April 2010
CAD 1 and CCR 2 protein complex formation in monolignol biosynthesis in Populus trichocarpa journal October 2018
Combining enhanced biomass density with reduced lignin level for improved forage quality journal July 2015
Novel seed coat lignins in the Cactaceae: structure, distribution and implications for the evolution of lignin diversity journal November 2012
CCR1, an enzyme required for lignin biosynthesis in Arabidopsis, mediates cell proliferation exit for leaf development journal July 2015
An essential role of caffeoyl shikimate esterase in monolignol biosynthesis in Medicago truncatula journal June 2016
Enzymatic basis for C‐lignin monomer biosynthesis in the seed coat of Cleome hassleriana journal May 2019
An “ideal lignin” facilitates full biomass utilization journal September 2018
Caffeoyl Shikimate Esterase (CSE) Is an Enzyme in the Lignin Biosynthetic Pathway in Arabidopsis journal August 2013
Lignin Valorization: Improving Lignin Processing in the Biorefinery journal May 2014
Monolignol Ferulate Transferase Introduces Chemically Labile Linkages into the Lignin Backbone journal April 2014
Reactive Oxygen Species in Plant Signaling journal April 2018
Altering the Cell Wall and Its Impact on Plant Disease: From Forage to Bioenergy journal August 2014
Lignin Biosynthesis journal June 2003
A horizontal gene transfer at the origin of phenylpropanoid metabolism: a key adaptation of plants to land journal January 2009
Recent advances in hydrogen peroxide imaging for biological applications journal October 2014
A 13C isotope labeling method for the measurement of lignin metabolic flux in Arabidopsis stems journal June 2018
Development and use of a switchgrass (Panicum virgatum L.) transformation pipeline by the BioEnergy Science Center to evaluate plants for reduced cell wall recalcitrance journal December 2017
Mathematical models of lignin biosynthesis journal February 2018
A dynamic model of lignin biosynthesis in Brachypodium distachyon journal September 2018
Integrative Analysis of Transgenic Alfalfa (Medicago sativa L.) Suggests New Metabolic Control Mechanisms for Monolignol Biosynthesis journal May 2011
Plant responses to stresses: role of ascorbate peroxidase in the antioxidant protection journal January 2012
Current Understanding of the Correlation of Lignin Structure with Biomass Recalcitrance journal November 2016
tRNAs as regulators of biological processes journal June 2014
Shikimate and Phenylalanine Biosynthesis in the Green Lineage journal January 2013
The Phenylpropanoid Case – It Is Transport That Matters journal November 2018
Role of lignification in plant defense journal February 2009
A dynamic model of lignin biosynthesis in Brachypodium distachyon dataset September 2018