Cellulose

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Cellulose[1]
Cellulose, a linear polymer of D-glucose units (two are shown) linked by β(1→4)-glycosidic bonds.
Three-dimensional structure of cellulose.
Identifiers
CAS number 9004-34-6 YesY
UNII SMD1X3XO9M YesY
EC-number 232-674-9
ChEMBL CHEMBL1201676 N
Properties
Molecular formula (C
6
H
10
O
5
)
n
Appearance white powder
Density 1.5 g/cm3
Melting point decomposes
Solubility in water none
Thermochemistry
Std enthalpy of
formation
ΔfHo298
−963 kJ mol−1
Std enthalpy of
combustion
ΔcHo298
−2828 kJ mol−1
Hazards
EU Index not listed
NFPA 704
Flammability code 1: Must be pre-heated before ignition can occur. Flash point over 93 °C (200 °F). E.g., canola oil Health code 1: Exposure would cause irritation but only minor residual injury. E.g., turpentine Reactivity code 0: Normally stable, even under fire exposure conditions, and is not reactive with water. E.g., liquid nitrogen Special hazards (white): no codeNFPA 704 four-colored diamond
Related compounds
Related compounds Starch
Except where noted otherwise, data are given for materials in their standard state (at 25 °C (77 °F), 100 kPa)
 N (verify) (what is: YesY/N?)
Infobox references

Cellulose is an organic compound with the formula (C
6
H
10
O
5
)
n
, a polysaccharide consisting of a linear chain of several hundred to many thousands of β(1→4) linked D-glucose units.[2][3] Cellulose is an important structural component of the primary cell wall of green plants, many forms of algae and the oomycetes. Some species of bacteria secrete it to form biofilms.[4] Cellulose is the most abundant organic polymer on Earth.[5] The cellulose content of cotton fiber is 90%, that of wood is 40–50% and that of dried hemp is approximately 45%.[6][7][8]

Cellulose is mainly used to produce paperboard and paper. Smaller quantities are converted into a wide variety of derivative products such as cellophane and rayon. Conversion of cellulose from energy crops into biofuels such as cellulosic ethanol is under investigation as an alternative fuel source. Cellulose for industrial use is mainly obtained from wood pulp and cotton.[5]

Some animals, particularly ruminants and termites, can digest cellulose with the help of symbiotic micro-organisms that live in their guts, such as Trichonympha. In humans, cellulose acts as a hydrophilic bulking agent for feces and is often referred to as a "dietary fiber".

History[edit]

Cellulose was discovered in 1838 by the French chemist Anselme Payen, who isolated it from plant matter and determined its chemical formula.[2][9][10] Cellulose was used to produce the first successful thermoplastic polymer, celluloid, by Hyatt Manufacturing Company in 1870. Production of rayon ("artificial silk") from cellulose began in the 1890s and cellophane was invented in 1912. Hermann Staudinger determined the polymer structure of cellulose in 1920. The compound was first chemically synthesized (without the use of any biologically derived enzymes) in 1992, by Kobayashi and Shoda.[11]

The arrangement of cellulose and other polysaccharides in a plant cell wall.

Structure and properties[edit]

Cellulose has no taste, is odorless, is hydrophilic with the contact angle of 20–30,[12] is insoluble in water and most organic solvents, is chiral and is biodegradable. It can be broken down chemically into its glucose units by treating it with concentrated acids at high temperature.

Cellulose is derived from D-glucose units, which condense through β(1→4)-glycosidic bonds. This linkage motif contrasts with that for α(1→4)-glycosidic bonds present in starch, glycogen, and other carbohydrates. Cellulose is a straight chain polymer: unlike starch, no coiling or branching occurs, and the molecule adopts an extended and rather stiff rod-like conformation, aided by the equatorial conformation of the glucose residues. The multiple hydroxyl groups on the glucose from one chain form hydrogen bonds with oxygen atoms on the same or on a neighbor chain, holding the chains firmly together side-by-side and forming microfibrils with high tensile strength. This confers tensile strength in cell walls, where cellulose microfibrils are meshed into a polysaccharide matrix.

A triple strand of cellulose showing the hydrogen bonds (cyan lines) between glucose strands

Compared to starch, cellulose is also much more crystalline. Whereas starch undergoes a crystalline to amorphous transition when heated beyond 60–70 °C in water (as in cooking), cellulose requires a temperature of 320 °C and pressure of 25 MPa to become amorphous in water.[13]

Several different crystalline structures of cellulose are known, corresponding to the location of hydrogen bonds between and within strands. Natural cellulose is cellulose I, with structures Iα and Iβ. Cellulose produced by bacteria and algae is enriched in Iα while cellulose of higher plants consists mainly of Iβ. Cellulose in regenerated cellulose fibers is cellulose II. The conversion of cellulose I to cellulose II is irreversible, suggesting that cellulose I is metastable and cellulose II is stable. With various chemical treatments it is possible to produce the structures cellulose III and cellulose IV.[14]

Many properties of cellulose depend on its chain length or degree of polymerization, the number of glucose units that make up one polymer molecule. Cellulose from wood pulp has typical chain lengths between 300 and 1700 units; cotton and other plant fibers as well as bacterial cellulose have chain lengths ranging from 800 to 10,000 units.[5] Molecules with very small chain length resulting from the breakdown of cellulose are known as cellodextrins; in contrast to long-chain cellulose, cellodextrins are typically soluble in water and organic solvents.

Plant-derived cellulose is usually found in a mixture with hemicellulose, lignin, pectin and other substances, while bacterial cellulose is quite pure, has a much higher water content and higher tensile strength due to higher chain lengths.[5]:3384

Cellulose is soluble in Schweizer's reagent, cupriethylenediamine (CED), cadmiumethylenediamine (Cadoxen), N-methylmorpholine N-oxide, and lithium chloride / dimethylacetamide.[15] This is used in the production of regenerated celluloses (such as viscose and cellophane) from dissolving pulp. Cellulose is also soluble in many kinds of ionic liquids.[16]

Cellulose consists of crystalline and amorphous regions. By treating it with strong acid, the amorphous regions can be broken up, thereby producing nanocrystalline cellulose, a novel material with many desirable properties.[17] Recently, nanocrystalline cellulose was used as the filler phase in bio-based polymer matrices to produce nanocomposites with superior thermal and mechanical properties.[18]

Processing[edit]

Assay[edit]

Given a cellulose-containing material, the carbohydrate portion that does not dissolve in a 17.5% solution of sodium hydroxide at 20 °C is α cellulose, which is true cellulose[clarification needed]. Acidification of the extract precipitates β cellulose. The portion that dissolves in base but does not precipitate with acid is γ cellulose[citation needed].

Cellulose can be assayed using a method described by Updegraff in 1969, where the fiber is dissolved in acetic and nitric acid to remove lignin, hemicellulose, and xylosans. The resulting cellulose is allowed to react with anthrone in sulfuric acid. The resulting coloured compound is assayed spectrophotometrically at a wavelength of approximately 635 nm.

In addition, cellulose is represented by the difference between acid detergent fiber (ADF) and acid detergent lignin (ADL).

Biosynthesis[edit]

In vascular plants cellulose is synthesized at the plasma membrane by rosette terminal complexes (RTCs). The RTCs are hexameric protein structures, approximately 25 nm in diameter, that contain the cellulose synthase enzymes that synthesise the individual cellulose chains.[19] Each RTC floats in the cell's plasma membrane and "spins" a microfibril into the cell wall.

RTCs contain at least three different cellulose synthases, encoded by CesA genes, in an unknown stoichiometry.[20] Separate sets of CesA genes are involved in primary and secondary cell wall biosynthesis. There are known to be about seven subfamilies in the CesA superfamily. These cellulose synthases use UDP-glucose to form the β(1→4)-linked cellulose.[21]

Cellulose synthesis requires chain initiation and elongation, and the two processes are separate. CesA glucosyltransferase initiates cellulose polymerization using a steroid primer, sitosterol-beta-glucoside, and UDP-glucose.[22] Cellulose synthase utilizes UDP-D-glucose precursors to elongate the growing cellulose chain. A cellulase may function to cleave the primer from the mature chain.

Cellulose is also synthesised by animals, particularly in the tests of ascidians (where the cellulose was historically termed "tunicine") although it is also a minor component of mammalian connective tissue.[23]

Breakdown (cellulolysis)[edit]

Cellulolysis is the process of breaking down cellulose into smaller polysaccharides called cellodextrins or completely into glucose units; this is a hydrolysis reaction. Because cellulose molecules bind strongly to each other, cellulolysis is relatively difficult compared to the breakdown of other polysaccharides.[24] However, this process can be significantly intensified in a proper solvent, e.g. in an ionic liquid. [25] Most mammals have only very limited ability to digest dietary fibres such as cellulose. Some ruminants like cows and sheep contain certain symbiotic anaerobic bacteria (like Cellulomonas) in the flora of the rumen, and these bacteria produce enzymes called cellulases that help the microorganism to break down cellulose; the breakdown products are then used by the bacteria for proliferation. The bacterial mass is later digested by the ruminant in its digestive system (stomach and small intestine). Similarly, lower termites contain in their hindguts certain flagellate protozoa which produce such enzymes; higher termites contain bacteria for the job. Some termites may also produce cellulase of their own.[26] Fungi, which in nature are responsible for recycling of nutrients, are also able to break down cellulose.

The enzymes utilized to cleave the glycosidic linkage in cellulose are glycoside hydrolases including endo-acting cellulases and exo-acting glucosidases. Such enzymes are usually secreted as part of multienzyme complexes that may include dockerins and carbohydrate-binding modules.[27]

Hemicellulose[edit]

Main article: Hemicellulose

Hemicellulose is a polysaccharide related to cellulose that comprises about 20% of the biomass of most plants. In contrast to cellulose, hemicellulose is derived from several sugars in addition to glucose, especially xylose but also including mannose, galactose, rhamnose, and arabinose. Hemicellulose consists of shorter chains – around 200 sugar units. Furthermore, hemicellulose is branched, whereas cellulose is unbranched.

Derivatives[edit]

The hydroxyl groups (-OH) of cellulose can be partially or fully reacted with various reagents to afford derivatives with useful properties like mainly cellulose esters and cellulose ethers (-OR). In principle, though not always in current industrial practice, cellulosic polymers are renewable resources.

Ester derivatives include:

Cellulose ester Reagent Example Reagent Group R
Organic esters Organic acids Cellulose acetate Acetic acid and acetic anhydride H or -(C=O)CH3
Cellulose triacetate Acetic acid and acetic anhydride -(C=O)CH3
Cellulose propionate Propanoic acid H or -(C=O)CH2CH3
Cellulose acetate propionate (CAP) Acetic acid and propanoic acid H or -(C=O)CH3 or -(C=O)CH2CH3
Cellulose acetate butyrate (CAB) Acetic acid and butyric acid H or -(C=O)CH3 or -(C=O)CH2CH2CH3
Inorganic esters Inorganic acids Nitrocellulose (cellulose nitrate) Nitric acid or another powerful nitrating agent H or -NO2
Cellulose sulfate Sulfuric acid or another powerful sulfuring agent H or -SO3H

The cellulose acetate and cellulose triacetate are film- and fiber-forming materials that find a variety of uses. The nitrocellulose was initially used as an explosive and was an early film forming material. With camphor, nitrocellulose gives celluloid.

Ether derivatives include:

Cellulose ethers Reagent Example Reagent Group R = H or Water solubility Application E number
Alkyl Halogenoalkanes Methylcellulose Chloromethane -CH3 Cold water soluble E461
Ethylcellulose Chloroethane -CH2CH3 Water insoluble A commercial thermoplastic used in coatings, inks, binders, and controlled-release drug tablets E462
Ethyl methyl cellulose Chloromethane and chloroethane -CH3 or -CH2CH3 E465
Hydroxyalkyl Epoxides Hydroxyethyl cellulose Ethylene oxide -CH2CH2OH Cold/hot water soluble Gelling and thickening agent
Hydroxypropyl cellulose (HPC) Propylene oxide -CH2CH(OH)CH3 Cold water soluble E463
Hydroxyethyl methyl cellulose Chloromethane and ethylene oxide -CH3 or -CH2CH2OH Cold water soluble Production of cellulose films
Hydroxypropyl methyl cellulose (HPMC) Chloromethane and propylene oxide -CH3 or -CH2CH(OH)CH3 Cold water soluble Viscosity modifier, gelling, foaming and binding agent E464
Ethyl hydroxyethyl cellulose Chloroethane and ethylene oxide -CH2CH3 or—CH2CH2OH E467
Carboxyalkyl Halogenated carboxylic acids Carboxymethyl cellulose (CMC) Chloroacetic acid -CH2COOH Cold/Hot water soluble Often used as its sodium salt, sodium carboxymethyl cellulose (NaCMC) E466

The sodium carboxymethyl cellulose can be cross-linked to give the croscarmellose sodium (E468) for use as a disintegrant in pharmaceutical formulations.

Applications[edit]

Cotton fibres represent the purest natural form of cellulose, containing more than 90% of this polysaccharide.

Cellulose for industrial use is mainly obtained from wood pulp and cotton.[5] The kraft process is used to separate cellulose from lignin, another major component of plant matter.

Paper products[edit]

Cellulose is the major constituent of paper, paperboard, and card stock.

Fibers[edit]

Cellulose is the main ingredient of textiles made from cotton, linen, and other plant fibers. It can be turned into rayon, an important fiber that has been used for textiles since the beginning of the 20th century. Both cellophane and rayon are known as "regenerated cellulose fibers"; they are identical to cellulose in chemical structure and are usually made from dissolving pulp via viscose. A more recent and environmentally friendly method to produce a form of rayon is the Lyocell process.

Consumables[edit]

Microcrystalline cellulose (E460i) and powdered cellulose (E460ii) are used as inactive fillers in drug tablets[28] and as thickeners and stabilizers in processed foods. Cellulose powder is, for example, used in Kraft's Parmesan cheese to prevent caking inside-of the package.

Science[edit]

Cellulose is used in the laboratory as a stationary phase for thin layer chromatography. Cellulose fibers are also used in liquid filtration, sometimes in combination with diatomaceous earth or other filtration media, to create a filter bed of inert material.

Energy crops[edit]

Main article: Energy crop

The major combustible component of non-food energy crops is cellulose, with lignin second. Non-food energy crops produce more usable energy than edible energy crops (which have a large starch component), but still compete with food crops for agricultural land and water resources.[29] Typical non-food energy crops include industrial hemp (though outlawed in some countries), switchgrass, Miscanthus, Salix(willow), and Populus (poplar) species.

A strand of cellulose (conformation Iα), showing the hydrogen bonds (dashed) within and between cellulose molecules.

Biofuel[edit]

TU-103, a strain of Clostridium bacteria found in zebra waste, can convert nearly any form of cellulose into butanol fuel.[30][31]

Building material[edit]

Hydroxyl bonding of cellulose in water produces a sprayable, moldable material as an alternative to the use of plastics and resins. The recyclable material can be made water- and fire-resistant. It provides sufficient strength for use as a building material.[32]

Cellulose insulation made from recycled paper is becoming popular as an environmentally preferable material for building insulation. It can be treated with boric acid as a fire retardant.

Miscellaneous[edit]

Cellulose can be converted into cellophane, a thin transparent film.

Cellulose is the raw material in the manufacture of nitrocellulose (cellulose nitrate) which is used in smokeless gunpowder. It is the base material for the celluloid that was used for photographic and movie films until the mid-1930s.

Cellulose is used to make water-soluble adhesives and binders such as methyl cellulose and carboxymethyl cellulose which are used in wallpaper paste.

Cellulose is further used to make hydrophilic and highly absorbent sponges.

References[edit]

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  2. ^ a b Crawford, R. L. (1981). Lignin biodegradation and transformation. New York: John Wiley and Sons. ISBN 0-471-05743-6. 
  3. ^ Updegraff DM (1969). "Semimicro determination of cellulose in biological materials". Analytical Biochemistry 32 (3): 420–424. doi:10.1016/S0003-2697(69)80009-6. PMID 5361396. 
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  20. ^ Taylor, N. G. (2003). "Interactions among three distinct CesA proteins essential for cellulose synthesis". Proceedings of the National Academy of Sciences 100 (3): 1450. doi:10.1073/pnas.0337628100. 
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External links[edit]