Abstract

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.

Highlights

  • Lignin is a major component of secondarily thickened plant cell walls and is considered to be the second most abundant biopolymer on the planet

  • We present several hypothetical models to illustrate these ideas and stimulate further research

  • Increased attention has been directed towards understanding lignin biosynthesis and its regulation over the past 10 years, largely driven by the aims of modifying the amount or composition of the polymer in plant cell walls to improve forage digestibility, facilitate bioprocessing of lignocellulose to liquid biofuels, or tailor the polymer itself for conversion to materials and/or bioproducts [9,10,11,12,13,14,15]

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Summary

Why the interest in lignin?

Lignin is the most abundant aromatic polymer produced in plants. It provides mechanical support and facilitates transport of water and solutes through the vascular system [1], as well as playing an important role in both passive and active defence [2,3,4,5]. Increased attention has been directed towards understanding lignin biosynthesis and its regulation over the past 10 years, largely driven by the aims of modifying the amount or composition of the polymer in plant cell walls to improve forage digestibility, facilitate bioprocessing of lignocellulose to liquid biofuels, or tailor the polymer itself for conversion to materials and/or bioproducts [9,10,11,12,13,14,15] These studies have drawn attention to the major gaps in our understanding of the processes by which the precursors of lignin (a). No other plant polymer appears to exhibit such structural flexibility, suggesting that, if natural and synthetic lignin building blocks have certain chemical features, both transport to the apoplast and subsequent polymerization are generally facile processes. Additional flexibility is suggested by the widely divergent lignin monomer compositions of different plant species, with gymnosperms such as pine (Pinus spp.) possessing lignin made of only G units, monocot species such as Z. mays having a preponderance of S units, and widely varying S/G ratios in dicotyledonous plants such as alfalfa (Medicago sativa), thale cress (Arabidopsis thaliana) and poplar (Populus spp.) (figure 2c)

The enigma of the esters pathway to monolignols
Old routes to lignin revisited
Monolignol biosynthesis and reactive oxygen
Monolignol transporters: cases for and against
Lignin initiation versus polymerization
Conclusion: still more questions than answers?
11. Ragauskas AJ et al 2014 Lignin valorization
13. Li Y et al 2018 An ‘ideal lignin’ facilitates full
28. Lam PY et al 2019 OsCAldOMT1 is a bifunctional
45. Saleme MD et al 2017 Silencing CAFFEOYL
Findings
81. Yan X et al 2019 CAD1 and CCR2 protein complex
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