Identifiers | |
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ChEMBL | |
ChemSpider |
|
ECHA InfoCard | 100.029.692 |
EC Number |
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E number | E460 (thickeners, ...) |
KEGG | |
PubChem CID | |
UNII | |
CompTox Dashboard (EPA) | |
Properties | |
(C 6H 10O 5) n | |
Molar mass | 162.1406 g/mol per glucose unit |
Appearance | white powder |
Density | 1.5 g/cm3 |
Melting point | 260–270 °C; 500–518 °F; 533–543 K (decomposes) [2] |
none | |
Thermochemistry | |
Std enthalpy of formation (ΔfH⦵298) | −963 kJ/mol[ clarification needed ] |
Std enthalpy of combustion (ΔcH⦵298) | −2828 kJ/mol[ clarification needed ] |
Hazards | |
NFPA 704 (fire diamond) | |
NIOSH (US health exposure limits): | |
PEL (Permissible) | TWA 15 mg/m3 (total) TWA 5 mg/m3 (resp) [2] |
REL (Recommended) | TWA 10 mg/m3 (total) TWA 5 mg/m3 (resp) [2] |
IDLH (Immediate danger) | N.D. [2] |
Related compounds | |
Related compounds | Starch |
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). |
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. [3] [4] 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. [5] Cellulose is the most abundant organic polymer on Earth. [6] The cellulose content of cotton fibre is 90%, that of wood is 40–50%, and that of dried hemp is approximately 57%. [7] [8] [9]
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 development as a renewable fuel source. Cellulose for industrial use is mainly obtained from wood pulp and cotton. [6] Cellulose is also greatly affected by direct interaction with several organic liquids. [10]
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 human nutrition, cellulose is a non-digestible constituent of insoluble dietary fiber, acting as a hydrophilic bulking agent for feces and potentially aiding in defecation.
Cellulose was discovered in 1838 by the French chemist Anselme Payen, who isolated it from plant matter and determined its chemical formula. [3] [11] [12] 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. [13]
Cellulose has no taste, is odorless, is hydrophilic with the contact angle of 20–30 degrees, [14] is insoluble in water and most organic solvents, is chiral and is biodegradable. It was shown to melt at 467 °C in pulse tests made by Dauenhauer et al. (2016). [15] It can be broken down chemically into its glucose units by treating it with concentrated mineral acids at high temperature. [16]
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 and glycogen. 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 neighbour 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. The high tensile strength of plant stems and of the tree wood also arises from the arrangement of cellulose fibers intimately distributed into the lignin matrix. The mechanical role of cellulose fibers in the wood matrix responsible for its strong structural resistance, can somewhat be compared to that of the reinforcement bars in concrete, lignin playing here the role of the hardened cement paste acting as the "glue" in between the cellulose fibres. Mechanical properties of cellulose in primary plant cell wall are correlated with growth and expansion of plant cells. [17] Live fluorescence microscopy techniques are promising in investigation of the role of cellulose in growing plant cells. [18]
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. [19]
Several types of cellulose are known. These forms are distinguished according 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. [20]
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. [6] 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.
The chemical formula of cellulose is (C6H10O5)n where n is the degree of polymerization and represents the number of glucose groups. [21]
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. [6] : 3384
Cellulose consists of fibrils with crystalline and amorphous regions. These cellulose fibrils may be individualized by mechanical treatment of cellulose pulp, often assisted by chemical oxidation or enzymatic treatment, yielding semi-flexible cellulose nanofibrils generally 200 nm to 1 μm in length depending on the treatment intensity. [22] Cellulose pulp may also be treated with strong acid to hydrolyze the amorphous fibril regions, thereby producing short rigid cellulose nanocrystals a few 100 nm in length. [23] These nanocelluloses are of high technological interest due to their self-assembly into cholesteric liquid crystals, [24] production of hydrogels or aerogels, [25] use in nanocomposites with superior thermal and mechanical properties, [26] and use as Pickering stabilizers for emulsions. [27]
In 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. [28] 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 (Ces is short for "cellulose synthase") genes, in an unknown stoichiometry. [29] Separate sets of CesA genes are involved in primary and secondary cell wall biosynthesis. There are known to be about seven subfamilies in the plant CesA superfamily, some of which include the more cryptic, tentatively-named Csl (cellulose synthase-like) enzymes. These cellulose syntheses use UDP-glucose to form the β(1→4)-linked cellulose. [30]
Bacterial cellulose is produced using the same family of proteins, although the gene is called BcsA for "bacterial cellulose synthase" or CelA for "cellulose" in many instances. [31] In fact, plants acquired CesA from the endosymbiosis event that produced the chloroplast. [32] All cellulose synthases known belongs to glucosyltransferase family 2 (GT2). [31]
Cellulose synthesis requires chain initiation and elongation, and the two processes are separate. Cellulose synthase (CesA) initiates cellulose polymerization using a steroid primer, sitosterol-beta-glucoside, and UDP-glucose. It then utilises UDP-D-glucose precursors to elongate the growing cellulose chain. A cellulase may function to cleave the primer from the mature chain. [33]
Cellulose is also synthesised by tunicate animals, particularly in the tests of ascidians (where the cellulose was historically termed "tunicine" (tunicin)). [34]
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. [35] However, this process can be significantly intensified in a proper solvent, e.g. in an ionic liquid. [36]
Most mammals have limited ability to digest dietary fibre such as cellulose. Some ruminants like cows and sheep contain certain symbiotic anaerobic bacteria (such as Cellulomonas and Ruminococcus spp.) in the flora of the rumen, and these bacteria produce enzymes called cellulases that hydrolyze cellulose. The breakdown products are then used by the bacteria for proliferation. [37] The bacterial mass is later digested by the ruminant in its digestive system (stomach and small intestine). Horses use cellulose in their diet by fermentation in their hindgut. [38] Some termites contain in their hindguts certain flagellate protozoa producing such enzymes, whereas others contain bacteria or may produce cellulase. [39]
The enzymes used 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. [40]
At temperatures above 350 °C, cellulose undergoes thermolysis (also called 'pyrolysis'), decomposing into solid char, vapors, aerosols, and gases such as carbon dioxide. [41] Maximum yield of vapors which condense to a liquid called bio-oil is obtained at 500 °C. [42]
Semi-crystalline cellulose polymers react at pyrolysis temperatures (350–600 °C) in a few seconds; this transformation has been shown to occur via a solid-to-liquid-to-vapor transition, with the liquid (called intermediate liquid cellulose or molten cellulose) existing for only a fraction of a second. [43] Glycosidic bond cleavage produces short cellulose chains of two-to-seven monomers comprising the melt. Vapor bubbling of intermediate liquid cellulose produces aerosols, which consist of short chain anhydro-oligomers derived from the melt. [44]
Continuing decomposition of molten cellulose produces volatile compounds including levoglucosan, furans, pyrans, light oxygenates, and gases via primary reactions. [45] Within thick cellulose samples, volatile compounds such as levoglucosan undergo 'secondary reactions' to volatile products including pyrans and light oxygenates such as glycolaldehyde. [46]
Hemicelluloses are polysaccharides related to cellulose that comprises about 20% of the biomass of land plants. In contrast to cellulose, hemicelluloses are derived from several sugars in addition to glucose, especially xylose but also including mannose, galactose, rhamnose, and arabinose. Hemicelluloses consist of shorter chains – between 500 and 3000 sugar units. [47] Furthermore, hemicelluloses are branched, whereas cellulose is unbranched.
Cellulose is soluble in several kinds of media, several of which are the basis of commercial technologies. These dissolution processes are reversible and are used in the production of regenerated celluloses (such as viscose and cellophane) from dissolving pulp.
The most important solubilizing agent is carbon disulfide in the presence of alkali. Other agents include Schweizer's reagent, N-methylmorpholine N-oxide, and lithium chloride in dimethylacetamide. In general, these agents modify the cellulose, rendering it soluble. The agents are then removed concomitant with the formation of fibers. [48] Cellulose is also soluble in many kinds of ionic liquids. [49]
The history of regenerated cellulose is often cited as beginning with George Audemars, who first manufactured regenerated nitrocellulose fibers in 1855. [50] Although these fibers were soft and strong -resembling silk- they had the drawback of being highly flammable. Hilaire de Chardonnet perfected production of nitrocellulose fibers, but manufacturing of these fibers by his process was relatively uneconomical. [50] In 1890, L.H. Despeissis invented the cuprammonium process – which uses a cuprammonium solution to solubilize cellulose – a method still used today for production of artificial silk. [51] In 1891, it was discovered that treatment of cellulose with alkali and carbon disulfide generated a soluble cellulose derivative known as viscose. [50] This process, patented by the founders of the Viscose Development Company, is the most widely used method for manufacturing regenerated cellulose products. Courtaulds purchased the patents for this process in 1904, leading to significant growth of viscose fiber production. [52] By 1931, expiration of patents for the viscose process led to its adoption worldwide. Global production of regenerated cellulose fiber peaked in 1973 at 3,856,000 tons. [50]
Regenerated cellulose can be used to manufacture a wide variety of products. While the first application of regenerated cellulose was as a clothing textile, this class of materials is also used in the production of disposable medical devices as well as fabrication of artificial membranes. [52]
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, although 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 | Propionic 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 sulfating agent | H or −SO3H |
Cellulose acetate and cellulose triacetate are film- and fiber-forming materials that find a variety of uses. Nitrocellulose was initially used as an explosive and was an early film forming material. When plasticized with camphor, nitrocellulose gives celluloid.
Cellulose Ether [53] derivatives include:
Cellulose ethers | Reagent | Example | Reagent | Group R = H or | Water solubility | Application | E number |
---|---|---|---|---|---|---|---|
Alkyl | Halogenoalkanes | Methylcellulose | Chloromethane | −CH3 | Cold/Hot water-soluble [54] | E461 | |
Ethylcellulose (EC) | Chloroethane | −CH2CH3 | Water-insoluble | A commercial thermoplastic used in coatings, inks, binders, and controlled-release drug tablets, [55] also employed in the production of oleogels and bioplastics [56] | 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 [57] | |
Hydroxypropyl cellulose (HPC) | Propylene oxide | −CH2CH(OH)CH3 | Cold water-soluble | filming properties, coating properties, pharmaceuticals, cultural heritage restoration, electronic applications, cosmetic sector [58] [59] [60] [61] [62] | 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. Furthermore, by the covalent attachment of thiol groups to cellulose ethers such as sodium carboxymethyl cellulose, ethyl cellulose or hydroxyethyl cellulose mucoadhesive and permeation enhancing properties can be introduced. [63] [64] [65] Thiolated cellulose derivatives (see thiomers) exhibit also high binding properties for metal ions. [66] [67]
Cellulose for industrial use is mainly obtained from wood pulp and from cotton. [6]
Energy crops:
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. [73] Typical non-food energy crops include industrial hemp, switchgrass, Miscanthus , Salix (willow), and Populus (poplar) species. A strain of Clostridium bacteria found in zebra dung, can convert nearly any form of cellulose into butanol fuel. [74] [75] [76] [77]
Another possible application is as Insect repellents. [78]
A cell wall is a structural layer that surrounds some cell types, found immediately outside the cell membrane. It can be tough, flexible, and sometimes rigid. Primarily, it provides the cell with structural support, shape, protection, and functions as a selective barrier. Another vital role of the cell wall is to help the cell withstand osmotic pressure and mechanical stress. While absent in many eukaryotes, including animals, cell walls are prevalent in other organisms such as fungi, algae and plants, and are commonly found in most prokaryotes, with the exception of mollicute bacteria.
A hemicellulose is one of a number of heteropolymers, such as arabinoxylans, present along with cellulose in almost all terrestrial plant cell walls. Cellulose is crystalline, strong, and resistant to hydrolysis. Hemicelluloses are branched, shorter in length than cellulose, and also show a propensity to crystallize. They can be hydrolyzed by dilute acid or base as well as a myriad of hemicellulase enzymes.
Polysaccharides, or polycarbohydrates, are the most abundant carbohydrates found in food. They are long-chain polymeric carbohydrates composed of monosaccharide units bound together by glycosidic linkages. This carbohydrate can react with water (hydrolysis) using amylase enzymes as catalyst, which produces constituent sugars. They range in structure from linear to highly branched. Examples include storage polysaccharides such as starch, glycogen and galactogen and structural polysaccharides such as hemicellulose and chitin.
Fiber is a natural or artificial substance that is significantly longer than it is wide. Fibers are often used in the manufacture of other materials. The strongest engineering materials often incorporate fibers, for example carbon fiber and ultra-high-molecular-weight polyethylene.
Lignin is a class of complex organic polymers that form key structural materials in the support tissues of most plants. Lignins are particularly important in the formation of cell walls, especially in wood and bark, because they lend rigidity and do not rot easily. Chemically, lignins are polymers made by cross-linking phenolic precursors.
Pulp is a fibrous lignocellulosic material prepared by chemically, semi-chemically or mechanically producing cellulosic fibers from wood, fiber crops, waste paper, or rags. Mixed with water and other chemicals or plant-based additives, pulp is the major raw material used in papermaking and the industrial production of other paper products.
Cellulase is any of several enzymes produced chiefly by fungi, bacteria, and protozoans that catalyze cellulolysis, the decomposition of cellulose and of some related polysaccharides:
Lyocell is a semi-synthetic fiber used to make textiles for clothing and other purposes. It is a form of regenerated cellulose made by dissolving pulp and dry jet-wet spinning. Unlike rayon made by the more common viscose processes, Lyocell production does not use carbon disulfide, which is toxic to workers and the environment. Lyocell was originally trademarked as Tencel in 1982.
Amylopectin is a water-insoluble polysaccharide and highly branched polymer of α-glucose units found in plants. It is one of the two components of starch, the other being amylose.
Cellulosic ethanol is ethanol produced from cellulose rather than from the plant's seeds or fruit. It can be produced from grasses, wood, algae, or other plants. It is generally discussed for use as a biofuel. The carbon dioxide that plants absorb as they grow offsets some of the carbon dioxide emitted when ethanol made from them is burned, so cellulosic ethanol fuel has the potential to have a lower carbon footprint than fossil fuels.
A pulp mill is a manufacturing facility that converts wood chips or other plant fiber sources into a thick fiber board which can be shipped to a paper mill for further processing. Pulp can be manufactured using mechanical, semi-chemical, or fully chemical methods. The finished product may be either bleached or non-bleached, depending on the customer requirements.
Natural fibers or natural fibres are fibers that are produced by geological processes, or from the bodies of plants or animals. They can be used as a component of composite materials, where the orientation of fibers impacts the properties. Natural fibers can also be matted into sheets to make paper or felt.
Lignocellulose refers to plant dry matter (biomass), so called lignocellulosic biomass. It is the most abundantly available raw material on the Earth for the production of biofuels. It is composed of two kinds of carbohydrate polymers, cellulose and hemicellulose, and an aromatic-rich polymer called lignin. Any biomass rich in cellulose, hemicelluloses, and lignin are commonly referred to as lignocellulosic biomass. Each component has a distinct chemical behavior. Being a composite of three very different components makes the processing of lignocellulose challenging. The evolved resistance to degradation or even separation is referred to as recalcitrance. Overcoming this recalcitrance to produce useful, high value products requires a combination of heat, chemicals, enzymes, and microorganisms. These carbohydrate-containing polymers contain different sugar monomers and they are covalently bound to lignin.
Biotextiles are specialized materials engineered from natural or synthetic fibers. These textiles are designed to interact with biological systems, offering properties such as biocompatibility, porosity, and mechanical strength or are designed to be environmentally friendly for typical household applications. There are several uses for biotextiles since they are a broad category. The most common uses are for medical or household use. However, this term may also refer to textiles constructed from biological waste product. These biotextiles are not typically used for industrial purposes.
The UDP-forming form of cellulose synthase is the main enzyme that produces cellulose. Systematically, it is known as UDP-glucose:(1→4)-β-D-glucan 4-β-D-glucosyltransferase in enzymology. It catalyzes the chemical reaction:
Cellulose fibers are fibers made with ethers or esters of cellulose, which can be obtained from the bark, wood or leaves of plants, or from other plant-based material. In addition to cellulose, the fibers may also contain hemicellulose and lignin, with different percentages of these components altering the mechanical properties of the fibers.
Bioproducts or bio-based products are materials, chemicals and energy derived from renewable biological material.
Bacterial cellulose is an organic compound with the formula (C
6H
10O
5)
n produced by certain types of bacteria. While cellulose is a basic structural material of most plants, it is also produced by bacteria, principally of the genera Komagataeibacter, Acetobacter, Sarcina ventriculi and Agrobacterium. Bacterial, or microbial, cellulose has different properties from plant cellulose and is characterized by high purity, strength, moldability and increased water holding ability. In natural habitats, the majority of bacteria synthesize extracellular polysaccharides, such as cellulose, which form protective envelopes around the cells. While bacterial cellulose is produced in nature, many methods are currently being investigated to enhance cellulose growth from cultures in laboratories as a large-scale process. By controlling synthesis methods, the resulting microbial cellulose can be tailored to have specific desirable properties. For example, attention has been given to the bacteria Komagataeibacter xylinus due to its cellulose's unique mechanical properties and applications to biotechnology, microbiology, and materials science.
Extracellular enzymes or exoenzymes are synthesized inside the cell and then secreted outside the cell, where their function is to break down complex macromolecules into smaller units to be taken up by the cell for growth and assimilation. These enzymes degrade complex organic matter such as cellulose and hemicellulose into simple sugars that enzyme-producing organisms use as a source of carbon, energy, and nutrients. Grouped as hydrolases, lyases, oxidoreductases and transferases, these extracellular enzymes control soil enzyme activity through efficient degradation of biopolymers.
Paul Dauenhauer, a chemical engineer and MacArthur Fellow, is the Lanny & Charlotte Schmidt Professor at the University of Minnesota (UMN). He is recognized for his research in catalysis science and engineering, especially, his contributions to the understanding of the catalytic breakdown of cellulose to renewable chemicals, the invention of oleo-furan surfactants, and the development of catalytic resonance theory and programmable catalysts.