Sulfation

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Sulfation is the chemical reaction that entails the addition of SO3 group. In principle, many sulfations would involve reactions of sulfur trioxide (SO3). In practice, most sulfations are effected less directly. Regardless of the mechanism, the installation of a sulfate-like group on a substrate leads to substantial changes.

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Sulfation in industry

Sulfation of calcium oxides

Sulfation is a process used to remove "sulfur" from the combustion of fossil fuels. The goal is to minimize the pollution by the combusted gases. Combustion of sulfur-containing fuels releases sulfur dioxide, which, in the atmosphere, oxidizes to the equivalent of sulfuric acid, which is corrosive. To minimize the problem, the combustion is often conducted in the presence of calcium oxide or calcium carbonate, which, directly or indirectly, bind sulfur dioxide and some oxygen to give calcium sulfite. [1] The net reaction is:

CaO + SO2 → CaSO3
2 CaSO3 + O2 → 2 CaSO4

or the net reaction is sulfation, the addition of SO3:

CaO + SO3 → CaSO3

In the idealized scenario, the calcium sulfate (gypsum) is used as a construction material or, less desirably, deposited in a landfill.

Other inorganic sulfations

Detergents, cosmetics, etc.

Sulfation is widely used in the production of consumer products such as detergents, shampoos, and cosmetics. Since the sulfate group is highly polar, its conjugation to a lipophilic "tail" gives surfacant-like properties. Well known sulfates are sodium lauryl sulfate and sodium laureth sulfate. [2]

Alkylsulfate are produced from alcohols by reaction with chlorosulfuric acid: [3]

ClSO3H + RCH2OH → ROSO3H + HCl

Alternatively, alcohols can be sulfated to the half sulfate esters using sulfur trioxide. The reaction proceeds by initial formation of the pyrosulfate:

2 SO3 + RCH2OH → RCH2OSO2−O−SO3H
RCH2OSO2−O−SO3H → RCH2OSO3H + SO3

Several million tons of fatty acid sulfates are produced in this way annually. The most common example is sodium dodecylsulfate (SDS) derived from lauryl alcohol. [4]

Sulfation in biology

Heparin, a naturally occurring sulfated sugar is used in the treatment of heart attacks. Heparin General Structure V.1.svg
Heparin, a naturally occurring sulfated sugar is used in the treatment of heart attacks.

In biology, sulfation is typically effected by sulfotransferases, which catalyze the transfer of the equivalent of sulfur trioxide to substrate alcohols and phenols, converting the latter to sulfate esters. [5] [6] The source of the SO3 group is usually 3'-phosphoadenosine-5'-phosphosulfate (PAPS). When the substrate is an amine, the result is a sulfamate. Sulfation is one of the principal routes for post-translational modification of proteins. [7]

Sulfation is involved in a variety of biological processes, including detoxification, hormone regulation, molecular recognition, cell signaling, and viral entry into cells. [6] It is among the reactions in phase II drug metabolism, frequently effective in rendering a xenobiotic less active from a pharmacological and toxicological standpoint, but sometimes playing a role in the activation of xenobiotics (e.g. aromatic amines, methyl-substituted polycyclic aromatic hydrocarbons). Sulfate is part of sulfolipids, such as sulfatides, which constitute 20% of the galactolipids in myelin. Another example of biological sulfation is in the synthesis of sulfonated glycosaminoglycans, such as heparin, heparan sulfate, chondroitin sulfate, and dermatan sulfate. Sulfation is also a possible posttranslational modification of proteins.

Tyrosine sulfation

Tyrosine sulfation is a posttranslational modification in which a tyrosine residue of a protein is sulfated by a tyrosylprotein sulfotransferase (TPST) typically in the Golgi apparatus. Secreted proteins and extracellular parts of membrane proteins that pass through the Golgi apparatus may be sulfated. Sulfation occurs in animals and plants but not in prokaryotes or in yeasts. Sulfation sites are tyrosine residues exposed on the surface of the protein typically surrounded by acidic residues. The function of sulfation remains uncertain. [7]

Regulation of tyrosine sulfation

Very limited evidence suggests that the TPST genes are subject to transcriptional regulation and tyrosine O-sulfate is very stable and cannot be easily degraded by mammalian sulfatases. Tyrosine O-sulfation is an irreversible process in vivo. An antibody called PSG2 shows high sensitivity and specificity for epitopes containing sulfotyrosine independent of the sequence context. New tools are being developed to study TPST's, using synthetic peptides and small molecule screens. [8]

Seagrasses

Many edible seaweeds are composed on highly sulfated polysaccharides. [9] The evolution of several sulfotransferases appears to have facilitated the adaptation of the terrestrial ancestors of seagrasses to a new marine habitat. [10] [11]

See also

Related Research Articles

<span class="mw-page-title-main">Oxide</span> Chemical compound where oxygen atoms are combined with atoms of other elements

An oxide is a chemical compound containing at least one oxygen atom and one other element in its chemical formula. "Oxide" itself is the dianion of oxygen, an O2– ion with oxygen in the oxidation state of −2. Most of the Earth's crust consists of oxides. Even materials considered pure elements often develop an oxide coating. For example, aluminium foil develops a thin skin of Al2O3 that protects the foil from further oxidation.

<span class="mw-page-title-main">Sulfuric acid</span> Chemical compound (H₂SO₄)

Sulfuric acid or sulphuric acid, known in antiquity as oil of vitriol, is a mineral acid composed of the elements sulfur, oxygen, and hydrogen, with the molecular formula H2SO4. It is a colorless, odorless, and viscous liquid that is miscible with water.

Sodium dodecyl sulfate (SDS) or sodium lauryl sulfate (SLS), sometimes written sodium laurilsulfate, is an organic compound with the formula CH3(CH2)11OSO3Na and structure H3C−(CH2)11−O−S(=O)2−O−Na+. It is an anionic surfactant used in many cleaning and hygiene products. This compound is the sodium salt of the 12-carbon organosulfate. Its hydrocarbon tail combined with a polar "headgroup" give the compound amphiphilic properties that make it useful as a detergent. SDS is also component of mixtures produced from inexpensive coconut and palm oils. SDS is a common component of many domestic cleaning, personal hygiene and cosmetic, pharmaceutical, and food products, as well as of industrial and commercial cleaning and product formulations.

In chemistry, a hydration reaction is a chemical reaction in which a substance combines with water. In organic chemistry, water is added to an unsaturated substrate, which is usually an alkene or an alkyne. This type of reaction is employed industrially to produce ethanol, isopropanol, and butan-2-ol.

Sulfur trioxide (alternative spelling sulphur trioxide, also known as nisso sulfan) is the chemical compound with the formula SO3. It has been described as "unquestionably the most [economically] important sulfur oxide". It is prepared on an industrial scale as a precursor to sulfuric acid.

<span class="mw-page-title-main">Calcium sulfate</span> Laboratory and industrial chemical

Calcium sulfate (or calcium sulphate) is the inorganic compound with the formula CaSO4 and related hydrates. In the form of γ-anhydrite (the anhydrous form), it is used as a desiccant. One particular hydrate is better known as plaster of Paris, and another occurs naturally as the mineral gypsum. It has many uses in industry. All forms are white solids that are poorly soluble in water. Calcium sulfate causes permanent hardness in water.

<span class="mw-page-title-main">Ammonium sulfate</span> Chemical compound

Ammonium sulfate (American English and international scientific usage; ammonium sulphate in British English); (NH4)2SO4, is an inorganic salt with a number of commercial uses. The most common use is as a soil fertilizer. It contains 21% nitrogen and 24% sulfur.

In chemistry, a dehydration reaction is a chemical reaction that involves the loss of water from the reacting molecule or ion. Dehydration reactions are common processes, the reverse of a hydration reaction.

<span class="mw-page-title-main">Sulfonic acid</span> Organic compounds with the structure R−S(=O)2−OH

In organic chemistry, sulfonic acid refers to a member of the class of organosulfur compounds with the general formula R−S(=O)2−OH, where R is an organic alkyl or aryl group and the S(=O)2(OH) group a sulfonyl hydroxide. As a substituent, it is known as a sulfo group. A sulfonic acid can be thought of as sulfuric acid with one hydroxyl group replaced by an organic substituent. The parent compound is the parent sulfonic acid, HS(=O)2(OH), a tautomer of sulfurous acid, S(=O)(OH)2. Salts or esters of sulfonic acids are called sulfonates.

Dodecanol, or lauryl alcohol, is an organic compound produced industrially from palm kernel oil or coconut oil. It is a fatty alcohol. Sulfate esters of lauryl alcohol, especially sodium lauryl sulfate, are very widely used as surfactants. Sodium lauryl sulfate and the related dodecanol derivatives ammonium lauryl sulfate and sodium laureth sulfate are all used in shampoos. Dodecanol is tasteless, colorless, and has a floral odor.

In biochemistry, tyrosine sulfation is a posttranslational modification where a sulfate group is added to a tyrosine residue of a protein molecule. Secreted proteins and extracellular parts of membrane proteins that pass through the Golgi apparatus may be sulfated. Sulfation was first discovered by Bettelheim in bovine fibrinopeptide B in 1954 and later found to be present in animals and plants but not in prokaryotes or in yeast.

<span class="mw-page-title-main">Isethionic acid</span> Chemical compound

Isethionic acid is an organosulfur compound containing an alkylsulfonic acid located beta to a hydroxy group. Its discovery is generally attributed to Heinrich Gustav Magnus, who prepared it by the action of solid sulfur trioxide on ethanol in 1833. It is a white water-soluble solid used in the manufacture of certain surfactants and in the industrial production of taurine. It is most commonly available in the form of its sodium salt.

<span class="mw-page-title-main">Triflic acid</span> Chemical compound

Triflic acid, the short name for trifluoromethanesulfonic acid, TFMS, TFSA, HOTf or TfOH, is a sulfonic acid with the chemical formula CF3SO3H. It is one of the strongest known acids. Triflic acid is mainly used in research as a catalyst for esterification. It is a hygroscopic, colorless, slightly viscous liquid and is soluble in polar solvents.

<span class="mw-page-title-main">Chlorosulfuric acid</span> Chemical compound

Chlorosulfuric acid (IUPAC name: sulfurochloridic acid) is the inorganic compound with the formula HSO3Cl. It is also known as chlorosulfonic acid, being the sulfonic acid of chlorine. It is a distillable, colorless liquid which is hygroscopic and a powerful lachrymator. Commercial samples usually are pale brown or straw colored.

<span class="mw-page-title-main">Sulfotransferase</span> Class of enzymes which transfer a sulfo group (–SO3) between molecules

In biochemistry, sulfotransferases (SULTs) are transferase enzymes that catalyze the transfer of a sulfo group from a donor molecule to an acceptor alcohol or amine. The most common sulfo group donor is 3'-phosphoadenosine-5'-phosphosulfate (PAPS). In the case of alcohol as acceptor, the product is a sulfate :

<span class="mw-page-title-main">Organosulfate</span> Organic compounds of the form R–O–SO₃ (charge –1)

In organosulfur chemistry, organosulfates are a class of organic compounds sharing a common functional group with the structure R−O−SO−3. The SO4 core is a sulfate group and the R group is any organic residue. All organosulfates are formally esters derived from alcohols and sulfuric acid although many are not prepared in this way. Many sulfate esters are used in detergents, and some are useful reagents. Alkyl sulfates consist of a hydrophobic hydrocarbon chain, a polar sulfate group and either a cation or amine to neutralize the sulfate group. Examples include: sodium lauryl sulfate and related potassium and ammonium salts.

<span class="mw-page-title-main">Wenker synthesis</span>

The Wenker synthesis is an organic reaction converting a beta amino alcohol to an aziridine with the help of sulfuric acid. It is used industrially for the synthesis of aziridine itself.

<span class="mw-page-title-main">Tyrosylprotein sulfotransferase</span> Enzyme

Tyrosylprotein sulfotransferase is an enzyme that catalyzes tyrosine sulfation.

<span class="mw-page-title-main">Calcium sulfite</span> Chemical compound

Calcium sulfite, or calcium sulphite, is a chemical compound, the calcium salt of sulfite with the formula CaSO3·x(H2O). Two crystalline forms are known, the hemihydrate and the tetrahydrate, respectively CaSO3·½(H2O) and CaSO3·4(H2O). All forms are white solids. It is most notable as the product of flue-gas desulfurization.

<span class="mw-page-title-main">Pyrosulfate</span>

In chemistry, disulfate or pyrosulfate is the anion with the molecular formula S
2O2−
7. Disulfate is the IUPAC name. It has a dichromate-like structure and can be visualised as two corner-sharing SO4 tetrahedra, with a bridging oxygen atom. In this anion, sulfur has an oxidation state of +6. Disulfate is the conjugate base of the hydrogen disulfate (hydrogen pyrosulfate) ion HS
2O−
7, which in turn is the conjugate base of disulfuric acid (pyrosulfuric acid).

References

  1. ↑ Anthony, E.J.; Granatstein, D.L. (2001). "Sulfation phenomena in fluidized bed combustion systems". Progress in Energy and Combustion Science. 27 (2): 215–236. doi:10.1016/S0360-1285(00)00021-6.
  2. ↑ Eduard Smulders, Wolfgang von Rybinski, Eric Sung, Wilfried Rähse, Josef Steber, Frederike Wiebel, Anette Nordskog "Laundry Detergents" in Ullmann's Encyclopedia of Industrial Chemistry 2007, Wiley-VCH, Weinheim. doi : 10.1002/14356007.a08_315.pub2.
  3. ↑ Klaus Noweck, Wolfgang Grafahrend, "Fatty Alcohols" in Ullmann’s Encyclopedia of Industrial Chemistry 2006, Wiley-VCH, Weinheim. doi : 10.1002/14356007.a10_277.pub2
  4. ↑ Holmberg, Krister (2019). "Surfactants". Ullmann's Encyclopedia of Industrial Chemistry. pp. 1–56. doi:10.1002/14356007.a25_747.pub2. ISBN   978-3-527-30673-2.
  5. ↑ Glatt, Hansruedi (2000). "Sulfotransferases in the bioactivation of xenobiotics". Chemico-Biological Interactions. 129 (1–2): 141–170. doi:10.1016/S0009-2797(00)00202-7. PMID   11154739.
  6. 1 2 Chapman, Eli; Best, Michael D.; Hanson, Sarah R.; Wong, Chi-Huey (2004-07-05). "Sulfotransferases: Structure, Mechanism, Biological Activity, Inhibition, and Synthetic Utility". Angewandte Chemie International Edition. 43 (27): 3526–3548. doi:10.1002/anie.200300631. ISSN   1521-3773. PMID   15293241.
  7. 1 2 Walsh, Gary; Jefferis, Roy (2006). "Post-translational modifications in the context of therapeutic proteins". Nature Biotechnology. 24 (10): 1241–1252. doi:10.1038/nbt1252. PMID   17033665. S2CID   33899490.
  8. ↑ Byrne, D. P. (2018). "New tools for evaluating protein tyrosine sulfation: tyrosylprotein sulfotransferases (TPSTs) are novel targets for RAF protein kinase inhibitors". Biochemical Journal. 475 (15): 2435–2455. doi: 10.1042/BCJ20180266 . PMC   6094398 . PMID   29934490.
  9. ↑ Jiao, Guangling; Yu, Guangli; Zhang, Junzeng; Ewart, H. (2011). "Chemical Structures and Bioactivities of Sulfated Polysaccharides from Marine Algae". Marine Drugs. 9 (2): 196–223. doi: 10.3390/md9020196 . PMC   3093253 . PMID   21566795.
  10. ↑ Olsen, Jeanine L.; et al. (2016). "The genome of the seagrass Zostera marina reveals angiosperm adaptation to the sea". Nature. 530 (7590): 331–335. Bibcode:2016Natur.530..331O. doi: 10.1038/nature16548 . hdl: 10754/595150 . PMID   26814964. S2CID   3713147.
  11. ↑ Pfeifer, Lukas; Classen, Birgit (2020). "The Cell Wall of Seagrasses: Fascinating, Peculiar and a Blank Canvas for Future Research". Frontiers in Plant Science. 11: 588754. doi: 10.3389/fpls.2020.588754 . PMC   7644952 . PMID   33193541.
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