Lignin

Lignin is a complex polymer of aromaticalcohols known as monolignols. It is most commonly derived from wood, and is an integral part of the secondary cell walls of plants and some algae. Lignin was first mentioned in 1813 by the Swiss botanist A. P. de Candolle, who described it as a fibrous, tasteless material, insoluble in water and alcohol but soluble in weak alkaline solutions, and which can be precipitated from solution using acid. He named the substance “lignine”, which is derived from the Latin word lignum, meaning wood. It is one of the most abundant organic polymers on Earth, exceeded only by cellulose. Lignin constitutes 30% of non-fossil organic carbon

The composition of lignin varies from species to species. An example of composition from an aspen sample is 63.4% carbon, 5.9% hydrogen, 0.7% ash, and 30% oxygen (by difference), corresponding approximately to the formula (C₃₁H₃₄O₁₁)_n. As a biopolymer, lignin is unusual because of its heterogeneity and lack of a defined primary structure. Its most commonly noted function is the support through strengthening of wood (xylem cells) in trees.

Global production of lignin is around 1.1 million metric tons per year and is used in a wide range of low volume, niche applications where the form but not the quality is important

Biological function

Lignin fills the spaces in the cell wall between cellulose, hemicellulose, and pectin components, especially in xylem tracheids, vessel elements and sclereid cells. It is covalently linked to hemicellulose and, therefore, crosslinks different plant polysaccharides, conferring mechanical strength to the cell wall and by extension the plant as a whole. It is particularly abundant in compression wood but scarce in tension wood, which are types of reaction wood.

Lignin plays a crucial part in conducting water in plant stems. The polysaccharide components of plant cell walls are highly hydrophilic and thus permeable to water, whereas lignin is more hydrophobic. The crosslinking of polysaccharides by lignin is an obstacle for water absorption to the cell wall. Thus, lignin makes it possible for the plant's vascular tissue to conduct water efficiently. Lignin is present in all vascular plants, but not in bryophytes, supporting the idea that the original function of lignin was restricted to water transport. However, it is present in red algae, which seems to suggest that the common ancestor of plants and red algae also synthesised lignin. This would suggest that its original function was structural; it plays this role in the red alga Calliarthron, where it supports joints between calcified segments. Another possibility is that the lignin in red algae and in plants are result of convergent evolution, and not of a common origin.

Ecological function

Lignin plays a significant role in the carbon cycle, sequestering atmospheric carbon into the living tissues of woody perennial vegetation. Lignin is one of the most slowly decomposing components of dead vegetation, contributing a major fraction of the material that becomes humus as it decomposes. The resulting soil humus, in general, increases the photosynthetic productivity of plant communities growing on a site as the site transitions from disturbed mineral soil through the stages of ecological succession, by providing increased cation exchange capacity in the soil and expanding the capacity of moisture retention between flood and drought conditions.

Economic significance

Highly lignified wood is durable and therefore a good raw material for many applications. It is also an excellent fuel, since lignin yields more energy when burned than cellulose. Mechanical, or high-yield pulpused to make newsprint contains most of the lignin originally present in the wood. This lignin is responsible for newsprint's yellowing with age. Lignin must be removed from the pulp before high-quality bleached paper can be manufactured.

In sulfite pulping, lignin is removed from wood pulp as sulfonates. These lignosulfonates have several uses:

·         Dispersants in high performance cement applications, water treatment formulations and textile dyes

·         Additives in specialty oil field applications and agriculturalchemicals

·         Raw materials for several chemicals, such as vanillin, DMSO, ethanol, xylitol sugar, and humic acid

·         Environmentally sustainable dust suppression agent for roads

The first investigations into commercial use of lignin were reported by Marathon Corporation, a paper company based in RothschildWisconsin, starting in 1927. The first class of products that showed promise were leather tanning agents. The lignin chemical business of Marathon was operated for many years as Marathon Chemicals. It is now known as LignoTech USA, Inc., and is owned by the Norwegiancompany Borregaard.

Lignin removed via the kraft process (sulfate pulping) is usually burned for its fuel value, providing energy to run the mill and its associated processes.

In 1998, a German company, Tecnaro, developed a process for turning lignin into a substance, called Arboform, which behaves identically to plastic for injection molding. Therefore, it can be used in place of plastic for several applications. When the item is discarded, it can be burned just like wood.

In 2007, lignin extracted from shrubby willow was successfully used to produce expanded polyurethane foam.

In 2012, it was shown carbon fiber can be produced from lignin instead of from fossil oil.

In 2013, the Flemish Institute for Biotechnology was supervising a trial of 448 poplar trees genetically engineered to produce less lignin so that they would be more suitable for conversion into bio-fuels

Biosynthesis

Lignin biosynthesis begins in the cytosol with the synthesis of glycosylated monolignols from the amino acid phenylalanine. These first reactions are shared with the phenylpropanoid pathway. The attached glucose renders them water soluble and less toxic. Once transported through the cell membrane to the apoplast, the glucose is removed and the polymerisation commences. Much about its anabolism is not understood even after more than a century of study.

The polymerisation step, that is a radical-radical coupling, is catalysedby oxidative enzymes. Both peroxidase and laccase enzymes are present in the plant cell walls, and it is not known whether one or both of these groups participates in the polymerisation. Low molecular weight oxidants might also be involved. The oxidative enzymecatalyses the formation of monolignol radicals. These radicals are often said to undergo uncatalyzed coupling to form the lignin polymer, but this hypothesis has been recently challenged. The alternative theory that involves an unspecified biological control is however not widely accepted.

Biodegradation

Biodegradation of lignin by brown rot, soft rot, or white rot fungi leads to destruction of wood on the forest floor and man-made structures such as fences and wooden buildings. However biodegradation of lignin is a necessary prerequisite for processing biofuel from plant raw materials. Current processing setups show some problematic residuals after processing the digestible or degradable contents. The improving of lignin degradation would drive the output from biofuel processing to better gain or better efficiency factor.

Lignin is indigestible by animal enzymes, but some fungi (such as theDryad's saddle) and bacteria are able to secrete ligninases (also named lignases) that can biodegrade the polymer. The details of the biodegradation are not yet well understood and the pathways depends on the type of wood decay. The enzymes involved may employ free radicals for depolymerization reactions. Well understood ligninolytic enzymes are manganese peroxidase and lignin peroxidase. Because it is cross-linked with the other cell wall components and is a bulky molecule, lignin minimizes the accessibility of cellulose and hemicellulose to microbial enzymes such as cellobiose dehydrogenase. Hence, in general lignin is associated with reduced digestibility of the overall plant biomass, which helps defend againstpathogens and pests. Additionally, Syringyl (S) lignol is more susceptible to degradation by fungal decay as it has fewer aryl-aryl bonds and a lower redox potential than guaiacyl units. This means that organic matter that is enriched with G lignol (like the bark of woody vascular plants) is more resistant to microbial attack.

Lignin degradation is done by micro-organisms like fungi and bacteria.Lignin peroxidase (also "ligninase", EC number 1.14.99) is ahemoprotein from the white-rot fungus Phanerochaete chrysosporium with a variety of lignin-degrading reactions, all dependent on hydrogen peroxide to incorporate molecular oxygen into reaction products. There are also several other microbial enzymes that are believed to be involved in lignin biodegradation, such as manganese peroxidase,laccase. It has been suggested that the ether bonds in lignin are cleaved by intramolecular epoxide formation when decayed by fungi.

Lignin-related chemicals can be further processed by bacteria. For instance, the aerobic Gram-negative soil bacterium Sphingomonas paucimobilis is able to degrade lignin-related biphenyl chemical compounds.

Chemical analysis

The conventional method for lignin quantitation in the pulp industry is the Klason lignin and acid-soluble lignin test, which is standardized according to SCAN or NREL procedure. The cellulose is first decrystallized and depolymerized by keeping the sample in 72% sulfuric acid at 30 C for 1 h. Then, the acid is diluted to 4% by adding water, and the depolymerization is completed by either boiling (100 C) for 4 h or pressure cooking at 2 bar (124 C) for 1 h. The acid is washed out and the sample dried. The residue that remain is termed Klason lignin. A part of the lignin, acid-soluble lignin (ASL) dissolves in the acid. ASL is quantified by the intensity of its UV absorption peak at 280 nm. The method is suited for wood lignins, but not equally well for varied lignins from different sources. The carbohydrate composition may be also analyzed from the Klason liquors, although there may be sugar breakdown products (furan and hydroxymethylfuran).

A solution of hydrochloric acid and phloroglucinol is used for the detection of lignin (Weisner test). A brilliant red color develops, owing to the presence of   coniferaldehyde  groups in the lignin.

Thioglycolysis is an analytical technique for lignin quantitation. Lignin structure can also be studied by computational simulation.

Thermochemolysis (chemical break down of a substance under vacuum and at high temperature) with tetramethylammonium hydroxide (TMAH) has also been used to analyse the ratios of lignols with fungal decay as well the ratio of the carboxylic acid (Ad) to aldehyde (Al) forms of the lignols (Ad/Al). Increases in the (Ad/Al) value indicate an oxidative cleavage reaction has occurred on the alkyl lignin side chain which has been shown to be a step in the decay of wood by many white-rot and some soft rot fungi.

Solid state ¹³C NMR has been used to look at the concentrations of lignin, as well as other major components in wood e.g. cellulose, and how that changes with microbial decay. Conventional solution-state NMR for lignin is possible. Howeeve, many intact lignins have a crosslinked, very high molar-mass fraction that is difficult to dissolve even for  functionalization.

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