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Alizarin (also known as 1,2-dihydroxyanthraquinone, Mordant Red 11, C.I. 58000, and Turkey Red) is an
organic compound In chemistry, organic compounds are generally any chemical compounds that contain carbon-hydrogen or carbon-carbon bonds. Due to carbon's ability to catenate (form chains with other carbon atoms), millions of organic compounds are known. Th ...
with formula that has been used throughout history as a prominent red
dye A dye is a colored substance that chemically bonds to the substrate to which it is being applied. This distinguishes dyes from pigments which do not chemically bind to the material they color. Dye is generally applied in an aqueous solution and ...
, principally for dyeing textile fabrics. Historically it was derived from the roots of plants of the
madder ''Rubia'' is the type genus of the Rubiaceae family of flowering plants, which also contains coffee. It contains around 80 species of perennial scrambling or climbing herbs and subshrubs native to the Old World. The genus and its best-know ...
genus.The primary madder species from which alizarin historically has been obtained is ''
Rubia tinctorum ''Rubia tinctorum'', the rose madder or common madder or dyer's madder, is a herbaceous perennial plant species belonging to the bedstraw and coffee family Rubiaceae. Description The common madder can grow up to 1.5 m in height. The evergree ...
''. See also
In 1869, it became the first natural dye to be produced synthetically. Alizarin is the main ingredient for the manufacture of the madder lake pigments known to painters as
rose madder Rose madder (also known as madder) is a red paint made from the pigment madder lake, a traditional lake pigment extracted from the common madder plant '' Rubia tinctorum''. Madder lake contains two organic red dyes: alizarin and purpurin. ...
and alizarin crimson. Alizarin in the most common usage of the term has a deep red color, but the term is also part of the name for several related non-red dyes, such as Alizarine Cyanine Green and Alizarine Brilliant Blue. A notable use of alizarin in modern times is as a
staining Staining is a technique used to enhance contrast in samples, generally at the microscopic level. Stains and dyes are frequently used in histology (microscopic study of biological tissues), in cytology (microscopic study of cells), and in th ...
agent in biological research because it stains free
calcium Calcium is a chemical element with the symbol Ca and atomic number 20. As an alkaline earth metal, calcium is a reactive metal that forms a dark oxide-nitride layer when exposed to air. Its physical and chemical properties are most similar ...
and certain calcium compounds a red or light purple color. Alizarin continues to be used commercially as a red textile dye, but to a lesser extent than in the past.


History

Madder has been cultivated as a
dyestuff A dye is a colored substance that chemically bonds to the substrate to which it is being applied. This distinguishes dyes from pigments which do not chemically bind to the material they color. Dye is generally applied in an aqueous solution and ...
since antiquity in central
Asia Asia (, ) is one of the world's most notable geographical regions, which is either considered a continent in its own right or a subcontinent of Eurasia, which shares the continental landmass of Afro-Eurasia with Africa. Asia covers an are ...
and
Egypt Egypt ( ar, مصر , ), officially the Arab Republic of Egypt, is a List of transcontinental countries, transcontinental country spanning the North Africa, northeast corner of Africa and Western Asia, southwest corner of Asia via a land bridg ...
, where it was grown as early as 1500 BC. Cloth dyed with madder root pigment was found in the tomb of the
Pharaoh Pharaoh (, ; Egyptian: '' pr ꜥꜣ''; cop, , Pǝrro; Biblical Hebrew: ''Parʿō'') is the vernacular term often used by modern authors for the kings of ancient Egypt who ruled as monarchs from the First Dynasty (c. 3150 BC) until th ...
Tutankhamun Tutankhamun (, egy, twt-ꜥnḫ-jmn), Egyptological pronunciation Tutankhamen () (), sometimes referred to as King Tut, was an Egyptian pharaoh who was the last of his royal family to rule during the end of the Eighteenth Dynasty (ruled ...
, in the ruins of
Pompeii Pompeii (, ) was an ancient city located in what is now the ''comune'' of Pompei near Naples in the Campania region of Italy. Pompeii, along with Herculaneum and many villas in the surrounding area (e.g. at Boscoreale, Stabiae), was burie ...
, and ancient
Athens Athens ( ; el, Αθήνα, Athína ; grc, Ἀθῆναι, Athênai (pl.) ) is both the capital and largest city of Greece. With a population close to four million, it is also the seventh largest city in the European Union. Athens dominates a ...
and
Corinth Corinth ( ; el, Κόρινθος, Kórinthos, ) is the successor to an ancient city, and is a former municipality in Corinthia, Peloponnese, which is located in south-central Greece. Since the 2011 local government reform, it has been part ...
. In the Middle Ages,
Charlemagne Charlemagne ( , ) or Charles the Great ( la, Carolus Magnus; german: Karl der Große; 2 April 747 – 28 January 814), a member of the Carolingian dynasty, was King of the Franks from 768, King of the Lombards from 774, and the first E ...
encouraged madder cultivation. Madder was widely used as a dye in Western Europe in the Late Medieval centuries. In 17th century England, alizarin was used as a red dye for the clothing of the parliamentary
New Model Army The New Model Army was a standing army formed in 1645 by the Parliamentarians during the First English Civil War, then disbanded after the Stuart Restoration in 1660. It differed from other armies employed in the 1639 to 1653 Wars of the Th ...
. The distinctive red color would continue to be worn for centuries (though also produced by other dyes such as
cochineal The cochineal ( , ; ''Dactylopius coccus'') is a scale insect in the suborder Sternorrhyncha, from which the natural dye carmine is derived. A primarily sessile parasite native to tropical and subtropical South America through North America ...
), giving English and later British soldiers the nickname of " redcoats". The madder dyestuff is combined with a dye
mordant A mordant or dye fixative is a substance used to set (i.e. bind) dyes on fabrics by forming a coordination complex with the dye, which then attaches to the fabric (or tissue). It may be used for dyeing fabrics or for intensifying stains in ...
. According to which mordant used, the resulting color may be anywhere from pink through purple to dark brown. In the 18th century the most valued color was a bright red known as "Turkey Red". The combination of mordants and overall technique used to obtain the Turkey Red originated in the Middle East or Turkey (hence the name). It was a complex and multi-step technique in its Middle Eastern formulation, some parts of which were unnecessary. The process was simplified in late 18th-century Europe. By 1804, a dye maker George Field in Britain had refined a technique to make ''
lake A lake is an area filled with water, localized in a basin, surrounded by land, and distinct from any river or other outlet that serves to feed or drain the lake. Lakes lie on land and are not part of the ocean, although, like the much large ...
'' madder by treating it with
alum An alum () is a type of chemical compound, usually a hydrated double sulfate salt of aluminium with the general formula , where is a monovalent cation such as potassium or ammonium. By itself, "alum" often refers to potassium alum, with the ...
, and an
alkali In chemistry, an alkali (; from ar, القلوي, al-qaly, lit=ashes of the saltwort) is a basic, ionic salt of an alkali metal or an alkaline earth metal. An alkali can also be defined as a base that dissolves in water. A solution of a ...
, that converts the water-soluble madder extract into a solid, insoluble pigment. This resulting ''madder lake'' has a longer-lasting color, and can be used more efficaciously, for example by blending it into a
paint Paint is any pigmented liquid, liquefiable, or solid mastic composition that, after application to a substrate in a thin layer, converts to a solid film. It is most commonly used to protect, color, or provide texture. Paint can be made in many ...
. Over the following years, it was found that other metal salts, including those containing
iron Iron () is a chemical element with symbol Fe (from la, ferrum) and atomic number 26. It is a metal that belongs to the first transition series and group 8 of the periodic table. It is, by mass, the most common element on Earth, right in ...
, tin, and
chromium Chromium is a chemical element with the symbol Cr and atomic number 24. It is the first element in group 6. It is a steely-grey, lustrous, hard, and brittle transition metal. Chromium metal is valued for its high corrosion resistance and hard ...
, could be used in place of alum to give madder-based pigments of various other colors. This general method of preparing lakes has been known for centuries but was simplified in the late 18th and early 19th centuries. In 1826, the
French French (french: français(e), link=no) may refer to: * Something of, from, or related to France ** French language, which originated in France, and its various dialects and accents ** French people, a nation and ethnic group identified with Franc ...
chemist
Pierre-Jean Robiquet Pierre Jean Robiquet (13 January 1780 – 29 April 1840) was a French chemist. He laid founding work in identifying amino acids, the fundamental building blocks of proteins. He did this through recognizing the first of them, asparagine, in 180 ...
found that madder root contained two colorants, the red alizarin and the more rapidly fading purpurin. The alizarin component became the first natural dye to be synthetically duplicated in 1868 when the
German German(s) may refer to: * Germany (of or related to) **Germania (historical use) * Germans, citizens of Germany, people of German ancestry, or native speakers of the German language ** For citizens of Germany, see also German nationality law **Ge ...
chemists Carl Graebe and
Carl Liebermann Carl Theodore Liebermann (23 February 1842 – 28 December 1914) was a German chemist and student of Adolf von Baeyer. Life Liebermann first studied at the University of Heidelberg where Robert Wilhelm Bunsen was teaching. He then joined th ...
, working for
BASF BASF SE () is a German multinational chemical company and the largest chemical producer in the world. Its headquarters is located in Ludwigshafen, Germany. The BASF Group comprises subsidiaries and joint ventures in more than 80 countries ...
, found a way to produce it from
anthracene Anthracene is a solid polycyclic aromatic hydrocarbon (PAH) of formula C14H10, consisting of three fused benzene rings. It is a component of coal tar. Anthracene is used in the production of the red dye alizarin and other dyes. Anthracene is co ...
. The
Bayer AG Bayer AG (, commonly pronounced ; ) is a German multinational pharmaceutical and biotechnology company and one of the largest pharmaceutical companies in the world. Headquartered in Leverkusen, Bayer's areas of business include pharmaceutica ...
company draws its roots from alizarin as well. About the same time, the
English English usually refers to: * English language * English people English may also refer to: Peoples, culture, and language * ''English'', an adjective for something of, from, or related to England ** English national ...
dye chemist
William Henry Perkin Sir William Henry Perkin (12 March 1838 – 14 July 1907) was a British chemist and entrepreneur best known for his serendipitous discovery of the first commercial synthetic organic dye, mauveine, made from aniline. Though he failed in trying ...
independently discovered the same synthesis, although the BASF group filed their patent before Perkin by one day. The subsequent discovery (made by Broenner and Gutzhow in 1871) that anthracene could be abstracted from
coal tar Coal tar is a thick dark liquid which is a by-product of the production of coke and coal gas from coal. It is a type of creosote. It has both medical and industrial uses. Medicinally it is a topical medication applied to skin to treat pso ...
further advanced the importance and affordability of alizarin's artificial synthesis. The synthetic alizarin could be produced for a fraction of the cost of the natural product, and the market for madder collapsed virtually overnight. The principal synthesis entailed oxidation of anthraquinone-2-sulfonic acid with
sodium nitrate Sodium nitrate is the chemical compound with the formula . This alkali metal nitrate salt is also known as Chile saltpeter (large deposits of which were historically mined in Chile) to distinguish it from ordinary saltpeter, potassium nitrate. ...
in concentrated
sodium hydroxide Sodium hydroxide, also known as lye and caustic soda, is an inorganic compound with the formula NaOH. It is a white solid ionic compound consisting of sodium cations and hydroxide anions . Sodium hydroxide is a highly caustic base and al ...
. Alizarin itself has been in turn largely replaced today by the more light-resistant
quinacridone Quinacridone is an organic compound used as a pigment. Numerous derivatives constitute the quinacridone pigment family, which finds extensive use in industrial colorant applications such as robust outdoor paints, inkjet printer ink, tattoo in ...
pigments developed at
DuPont DuPont de Nemours, Inc., commonly shortened to DuPont, is an American multinational chemical company first formed in 1802 by French-American chemist and industrialist Éleuthère Irénée du Pont de Nemours. The company played a major role in ...
in 1958.


Structure and properties

left, 136px, 1,4-Dihydroxyanthraquinone, also called quinizarin, is an isomer of alizarin. Alizarin is one of ten dihydroxyanthraquinone isomers. It is soluble in
hexane Hexane () is an organic compound, a straight-chain alkane with six carbon atoms and has the molecular formula C6H14. It is a colorless liquid, odorless when pure, and with boiling points approximately . It is widely used as a cheap, relative ...
and
chloroform Chloroform, or trichloromethane, is an organic compound with formula C H Cl3 and a common organic solvent. It is a colorless, strong-smelling, dense liquid produced on a large scale as a precursor to PTFE. It is also a precursor to various ...
, and can be obtained from the latter as red-purple crystals, melting point 277–278 °C. Alizarin changes color depending on the pH of the solution it is in, thereby making it a
pH indicator A pH indicator is a halochromic chemical compound added in small amounts to a solution so the pH (acidity or basicity) of the solution can be determined visually or spectroscopically by changes in absorption and/or emission properties. Hence, ...
.


Applications

Alizarin Red is used in a biochemical assay to determine, quantitatively by colorimetry, the presence of calcific deposition by cells of an
osteogenic Ossification (also called osteogenesis or bone mineralization) in bone remodeling is the process of laying down new bone material by cells named osteoblasts. It is synonymous with bone tissue formation. There are two processes resulting in the ...
lineage. As such it is an early stage marker (days 10–16 of in vitro culture) of matrix mineralization, a crucial step towards the formation of calcified
extracellular matrix In biology, the extracellular matrix (ECM), also called intercellular matrix, is a three-dimensional network consisting of extracellular macromolecules and minerals, such as collagen, enzymes, glycoproteins and hydroxyapatite that provide s ...
associated with true bone. Alizarin's abilities as a biological stain were first noted in 1567, when it was observed that when fed to animals, it stained their teeth and bones red. The chemical is now commonly used in medical studies involving calcium. Free (ionic) calcium forms precipitates with alizarin, and tissue block containing calcium stain red immediately when immersed in alizarin. Thus, both pure calcium and calcium in bones and other tissues can be stained. These alizarin-stained elements can be better visualized under fluorescent lights, excited by 440–460 nm. The process of staining calcium with alizarin works best when conducted in acidic solution (in many labs, it works better in pH 4.1 to 4.3). In clinical practice, it is used to stain
synovial fluid Synovial fluid, also called synovia, elp 1/sup> is a viscous, non-Newtonian fluid found in the cavities of synovial joints. With its egg white–like consistency, the principal role of synovial fluid is to reduce friction between the articul ...
to assess for basic
calcium phosphate The term calcium phosphate refers to a family of materials and minerals containing calcium ions (Ca2+) together with inorganic phosphate anions. Some so-called calcium phosphates contain oxide and hydroxide as well. Calcium phosphates are whi ...
crystals. Alizarin has also been used in studies involving bone growth, osteoporosis, bone marrow, calcium deposits in the vascular system, cellular signaling, gene expression, tissue engineering, and mesenchymal stem cells. In
geology Geology () is a branch of natural science concerned with Earth and other Astronomical object, astronomical objects, the features or rock (geology), rocks of which it is composed, and the processes by which they change over time. Modern geology ...
, it is used as a stain to differentiate the calcium carbonate
minerals In geology and mineralogy, a mineral or mineral species is, broadly speaking, a solid chemical compound with a fairly well-defined chemical composition and a specific crystal structure that occurs naturally in pure form.John P. Rafferty, ed ...
, especially
calcite Calcite is a carbonate mineral and the most stable polymorph of calcium carbonate (CaCO3). It is a very common mineral, particularly as a component of limestone. Calcite defines hardness 3 on the Mohs scale of mineral hardness, based on scratc ...
and
aragonite Aragonite is a carbonate mineral, one of the three most common naturally occurring crystal forms of calcium carbonate, (the other forms being the minerals calcite and vaterite). It is formed by biological and physical processes, including pre ...
in
thin section In optical mineralogy and petrography, a thin section (or petrographic thin section) is a thin slice of a rock or mineral sample, prepared in a laboratory, for use with a polarizing petrographic microscope, electron microscope and electron ...
or polished surfaces. Madder lake had been in use as a red pigment in paintings since antiquity. File:Red alizarin 1.jpg, Red alizarin staining of rat's embryonic bones for osteogenesis study File:N pectoralis.jpg, Red alizarin stained juvenile Roosterfish (''Nematistius pectoralis'') lit by fluorescent light. File:Johannes (Jan) Vermeer - Christ in the House of Martha and Mary - Google Art Project.jpg, Johannes Vermeer, Christ in the House of Martha and Mary, 1654-56. The red blouse of Mary is painted in madder lake File:Walraversijde18.jpg, Reconstruction blankets dyed with madder


See also

*
1,2,4-Trihydroxyanthraquinone 1,2,4-Trihydroxyanthraquinone, commonly called purpurin, is an anthraquinone. It is a naturally occurring red/yellow dye. It is formally derived from 9,10-anthraquinone by replacement of three hydrogen atoms by hydroxyl (OH) groups. Purpurin i ...
or purpurin, another red dye that occurs in madder root * Alizarine ink *
Aniline Aniline is an organic compound with the formula C6 H5 NH2. Consisting of a phenyl group attached to an amino group, aniline is the simplest aromatic amine. It is an industrially significant commodity chemical, as well as a versatile starti ...
* Dihydroxyanthraquinone *
Hydroxyanthraquinone A hydroxyanthraquinone (formula: C14H9O2(OH)) is any of several organic compounds that can be viewed as derivatives of an anthraquinone through replacement of one hydrogen atom (H) by a hydroxyl group (-OH). The IUPAC nomenclature recommends hydro ...
*
List of colors (compact) The following list shows a compact version of the colors in the list of colors A–F, G–M, and N–Z articles. The list shows the color swatch and its name. Hovering over the color box shows the HSV, RGB, and #hex values for the color i ...
*
List of dyes This is a list of dyes with Colour Index International generic names and numbers and CAS Registry numbers. Note * Synonyms should be treated with caution because they are often used inconsistently, see discussion page and external lin See also ...
* Diaphonization * Red pigments


References


Further reading

* Schweppe, H., and Winter, J. "Madder and Alizarin", in ''Artists’ Pigments: A Handbook of Their History and Characteristics, Vol. 3'': E.W. Fitzhugh (Ed.) Oxford University Press 1997, pp. 109–142


External links


Molecule of the day: Alizarin

Madder lake
Colourlex {{Authority control Anthraquinone dyes Catechols Chelating agents Dihydroxyanthraquinones Organic pigments 3-Hydroxypropenals within hydroxyquinones