Alizarin

Alizarin (also known as 1,2-dihydroxyanthraquinone, Mordant Red 11, C.I. 58000, and Turkey Red[1]) is an organic compound with formula C
14
H
8
O
4
that has been used throughout history as a prominent red dye, principally for dyeing textile fabrics. Historically it was derived from the roots of plants of the madder genus.[2] In 1869, it became the first natural dye to be produced synthetically.[3]

Alizarin is the main ingredient for the manufacture of the madder lake pigments known to painters as Rose madder 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 agent in biological research because it stains free calcium 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.

Alizarin
Skeletal formula of alizarin
Ball-and-stick model of alizarin
Sample of alizarin
Names
Preferred IUPAC name
1,2-Dihydroxyanthracene-9,10-dione
Other names
1,2-Dihydroxy-9,10-anthracenedione
1,2-Dihydroxyanthraquinone
Turkey red
Mordant red 11
Alizarin B
Alizarin red
Identifiers
3D model (JSmol)
ChEBI
ChEMBL
ChemSpider
ECHA InfoCard 100.000.711
KEGG
UNII
Properties
C14H8O4
Molar mass 240.214 g·mol−1
Appearance orange-red crystals or powder
Density 1.540 g/cm3
Melting point 279 to 283 °C (534 to 541 °F; 552 to 556 K)
Boiling point 430 °C (806 °F; 703 K)
slightly to sparingly soluble
Acidity (pKa) 6.94
Hazards
Safety data sheet External MSDS
R-phrases (outdated) R36 R37 R38
S-phrases (outdated) S26 S36
Related compounds
Related compounds
anthraquinone, anthracene
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

History

Madder has been cultivated as a dyestuff since antiquity in central Asia and Egypt, where it was grown as early as 1500 BC. Cloth dyed with madder root pigment was found in the tomb of the Pharaoh Tutankhamun and in the ruins of Pompeii and ancient Corinth. In the Middle Ages, Charlemagne encouraged madder cultivation. Madder was widely used as a dye in Western Europe in the Late Medieval centuries.[4] In 17th century England, alizarin was used as a red dye for the clothing of the parliamentary New Model Army. The distinctive red color would continue to be worn for centuries (though also produced by other dyes such as cochineal), giving English and later British soldiers the nickname of "redcoats".

Alizarin01
alizarin color

The madder dyestuff is combined with a dye mordant. 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.[5] 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 madder by treating it with alum, and an alkali,[6] 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. Over the following years, it was found that other metal salts, including those containing iron, tin, and chromium, 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[7] but was simplified in the late 18th and early 19th centuries.

In 1826, the French chemist Pierre-Jean Robiquet found that madder root contained two colorants, the red alizarin and the more rapidly fading purpurin.[8] The alizarin component became the first natural dye to be synthetically duplicated in 1868 when the German chemists Carl Graebe and Carl Liebermann, working for BASF, found a way to produce it from anthracene.[9] About the same time, the English dye chemist William Henry Perkin 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 further advanced the importance and affordability of alizarin's artificial synthesis.[10]

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 in concentrated sodium hydroxide. Alizarin itself has been in turn largely replaced today by the more light-resistant quinacridone pigments developed at DuPont in 1958.

Structure and properties

Alizarin is one of ten dihydroxyanthraquinone isomers. Its molecular structure can be viewed as being derived from anthraquinone by replacement of two neighboring hydrogen atoms (H) by hydroxyl groups (−OH).

It is soluble in hexane and chloroform, and can be obtained from the latter as red-purple crystals, melting point 277–278 °C.[2]

Alizarin changes color depending on the pH of the solution it is in, thereby making it a pH indicator.[11]

Applications

Alizarin Red is used in a biochemical assay to determine, quantitatively by colorimetry, the presence of calcific deposition by cells of an osteogenic 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 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[12]. 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).[13]

In clinical practice, it is used to stain synovial fluid to assess for basic calcium phosphate crystals.[14] 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.[13]

In geology, it is used as a stain to differentiate the calcium carbonate minerals, especially calcite and aragonite in thin section or polished surfaces.[15][16]

Madder lake had been in use as a red pigment in paintings since antiquity.[17]

Red alizarin 1

Red alizarin staining of rat's embryonic bones for osteogenesis study

N pectoralis

Red alizarin stained juvenile Roosterfish (Nematistius pectoralis) lit by fluorescent light. [18]

Johannes (Jan) Vermeer - Christ in the House of Martha and Mary - Google Art Project

Johannes Vermeer, Christ in the House of Martha and Mary, 1654-56. The red blouse of Mary is painted in madder lake

See also

References

  1. ^ SigmaAldrich Catalog: Alizarin
  2. ^ a b The primary madder species from which alizarin historically has been obtained is Rubia tinctorum. See also Vankar, P. S.; Shanker, R.; Mahanta, D.; Tiwari, S. C. (2008). "Ecofriendly Sonicator Dyeing of Cotton with Rubia cordifolia Linn. Using Biomordant". Dyes and Pigments. 76 (1): 207–212. doi:10.1016/j.dyepig.2006.08.023.
  3. ^ Bien, H.-S.; Stawitz, J.; Wunderlich, K. "Anthraquinone Dyes and Intermediates". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a02_355.
  4. ^ Many examples of the use of the word "madder", meaning the roots of the plant Rubia tinctorum used as a dye, are given in the Middle English Dictionary, a dictionary of late medieval English.
  5. ^ Lowengard, S. (2006). "Industry and Ideas: Turkey Red". The Creation of Color in 18th Century Europe. Gutenberg-E.org. ISBN 9780231503693. Additional 18th century history at "Turkey Red Dyeing in Blackley - The Delaunay Dyeworks". ColorantsInHistory.org.
  6. ^ George Field's notes are held at the Courtauld Institute of Art. See "FIELD, George (?1777-1854)". Retrieved 2012-08-04.
  7. ^ Thompson, D. V. (1956). The Materials and Techniques of Medieval Painting. Dover. pp. 115–124. ISBN 978-0-486-20327-0.
  8. ^ See:
  9. ^ Note:
    • In 1868, Graebe and Liebermann showed that alizarin can be converted into anthracene. See: C. Graebe and C. Liebermann (1868) "Ueber Alizarin, und Anthracen" (On alizarin and anthracene), Berichte der Deutschen chemischen Gesellschaft zu Berlin, 1 : 49-51.
    • In 1869, Graebe and Liebermann announced that they had succeeded in transforming anthracene into alizarin. See: C. Graebe and C. Liebermann (1869) "Ueber künstliche Bildung von Alizarin" (On the artificial formation of alizarin), Berichte der Deutschen chemischen Gesellschaft zu Berlin, 2 : 14.
    • For Graebe and Liebermann's original process for making alizarin from anthracene, see: Charles Graebe and Charles Liebermann, "Improved process of preparing alizarine," U.S. Patent no. 95,465 (issued: October 5, 1869). (See also their English patent, no. 3,850, issued December 18, 1868.)
    • A more efficient process for making alizarin from anthracene was developed by Caro, Graebe and Liebermann in 1870. See: H. Caro, C. Graebe, and C. Liebermann (1870) "Ueber Fabrikation von künstlichem Alizarin" (On the manufacture of artificial alizarin), Berichte der Deutschen chemischen Gesellschaft zu Berlin, 3 : 359-360.
  10. ^ Brönner, J.; Gutzkow, H. (1871). "Verfahren zur Darstellung von Anthracen aus dem Pech von Steinkohlentheer, und zur Darstellung von Farbstoffen aus Anthracen" [Process for Preparing Anthracene from Coal-Tar Pitch, and Preparation of Dye-Stuffs from Anthracene]. Dinglers Polytechnisches Journal (in German). 201: 545–546.
  11. ^ Meloan, S. N.; Puchtler, H.; Valentine, L. S. (1972). "Alkaline and Acid Alizarin Red S Stains for Alkali-Soluble and Alkali-Insoluble Calcium Deposits". Archives of Pathology. 93 (3): 190–197. PMID 4110754.
  12. ^ Smith, W. Leo; Buck, Chesney A.; Ornay, Gregory S.; Davis, Matthew P.; Martin, Rene P.; Gibson, Sarah Z.; Girard, Matthew G. (2018-08-20). "Improving Vertebrate Skeleton Images: Fluorescence and the Non-Permanent Mounting of Cleared-and-Stained Specimens". Copeia. 106 (3): 427–435. doi:10.1643/cg-18-047. ISSN 0045-8511.
  13. ^ a b Puchtler, H.; Meloan, S. N.; Terry, M. S. (1969). "On the History and Mechanism of Alizarin Red S Stains for Calcium". The Journal of Histochemistry and Cytochemistry. 17 (2): 110–124. doi:10.1177/17.2.110. PMID 4179464.
  14. ^ Paul, H.; Reginato, A. J.; Schumacher, H. R. (1983). "Alizarin Red S Staining as a Screening Test to Detect Calcium Compounds in Synovial Fluid". Arthritis and Rheumatism. 26 (2): 191–200. doi:10.1002/art.1780260211. PMID 6186260.
  15. ^ Green, O. R. (2001). A Manual of Practical Laboratory and Field Techniques in Palaeobiology. Springer. p. 56. ISBN 978-0-412-58980-5.
  16. ^ Dickson, J. A. D. (1966). "Carbonate identification and genesis as revealed by staining". Journal of Sedimentary Research. 36 (4): 491–505. doi:10.1306/74D714F6-2B21-11D7-8648000102C1865D.
  17. ^ 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, p. 111 – 112
  18. ^ Smith, W. Leo; Buck, Chesney A.; Ornay, Gregory S.; Davis, Matthew P.; Martin, Rene P.; Gibson, Sarah Z.; Girard, Matthew G. (2018-08-20). "Improving Vertebrate Skeleton Images: Fluorescence and the Non-Permanent Mounting of Cleared-and-Stained Specimens". Copeia. 106 (3): 427–435. doi:10.1643/cg-18-047. ISSN 0045-8511.

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

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 is also called verantin, smoke Brown G, hydroxylizaric acid, and C.I. 58205. It is a minor component of the classical lake pigment "madder lake" or Rose Madder.

1,3-Dihydroxyanthraquinone

1,3-Dihydroxyanthraquinone, also called purpuroxanthin or xanthopurpurin, is an organic compound with formula C14H8O4 that occurs in the plant Rubia cordifolia (Indian madder). It is one of ten dihydroxyanthraquinone isomers. Its molecular structure can be viewed as being derived from anthraquinone by replacement of two hydrogen atoms (H) by hydroxyl groups (-OH).

Xanthopurpurin occurs in small amounts (as a glycoside) in the root of the common madder plant, Rubia tinctorum, together with alizarin, purpurin and other anthraquinone derivatives.

Alizarin 2-beta-glucosyltransferase

In enzymology, an alizarin 2-beta-glucosyltransferase (EC 2.4.1.103) is an enzyme that catalyzes the chemical reaction

UDP-glucose + alizarin UDP + 1-hydroxy-2-(beta-D-glucosyloxy)-9,10-anthraquinone

Thus, the two substrates of this enzyme are UDP-glucose and alizarin, whereas its two products are UDP and 1-hydroxy-2-(beta-D-glucosyloxy)-9,10-anthraquinone.

This enzyme belongs to the family of glycosyltransferases, specifically the hexosyltransferases. The systematic name of this enzyme class is UDP-glucose:1,2-dihydroxy-9,10-anthraquinone 2-O-beta-D-glucosyltransferase. This enzyme is also called uridine diphosphoglucose-alizarin glucosyltransferase.

Alizarin Red S

Alizarin Red S (also known as C.I. Mordant Red 3, Alizarin Carmine, and C.I 58005. It is a water-soluble sodium salt of Alizarin with a chemical formula of C14H7NaO7S. Alizarin Red S was discovered by Graebe and Libermann in 1871. In the field of histology alizarin Red S is been used to stain calcium deposits in tissues, and in geology to stain and differentiate carbonate minerals.

Alizarin crimson

Alizarin crimson may refer to:

Alizarin crimson (color), a particular shade of red

Alizarin, a paint pigment

Alizarin crimson (color)

Alizarin crimson is a shade of red that is biased slightly more towards purple than towards orange on the color wheel and has a blue undertone. It is named after the organic dye alizarin, found in the madder plant, and the related synthetic lake pigment alizarin crimson (PR83 in the Color Index). Alizarin crimson paint was frequently used on Bob Ross' TV show, The Joy of Painting. William Henry Perkin had co-discovered a way to synthesize the pigment alizarin, which became known as the color alizarin crimson. Its consistency and lightfastness quickly made it a favourite red pigment for artists.

Alizarin crimson can create a wide range of rich, permanent purples and browns. The dye was prominently used for dying clothes and traces were found in Ancient Egypt, Persia and the ruins of Pompeii. By the seventh century BC, the dye had been made into a lake pigment and was used across Europe, the Middle East and Asia. By this time the use of madder dye and pigment were widespread, but they remained costly and time consuming to produce.

Alizarine Yellow R

Alizarine Yellow R is a yellow colored azo dye made by the diazo coupling reaction. It usually comes as a sodium salt. In its pure form it is a rust-colored solid. Its main use is as a pH indicator.

Alizarine ink

Alizarine ink was created in 1855 by Professor Leonhardi of Dresden, Germany, by adding alizarin dye (derived from the root of the madder plant) to conventional iron gall ink. This added an attractive coloration to the ink, which was quite popular until it was replaced by more modern chemical inks.An 1881 recipe for Alizarine ink may be found in the Household Cyclopedia of General Information.

Aluminium triacetate

Aluminium triacetate, formally named aluminium acetate, is a chemical compound with composition Al(CH3CO2)3. Under standard conditions it appears as a white, water-soluble solid that decomposes on heating at around 200 °C. The triacetate hydrolyses to a mixture of basic hydroxide / acetate salts, and multiple species co-exist in chemical equilibrium, particularly in aqueous solutions of the acetate ion; the name aluminium acetate is commonly used for this mixed system.

It has therapeutic applications for its anti-itching, astringent, and antiseptic properties, and, as an over-the-counter preparation like Burow's solution, it is used to treat ear infections. Burow's solution preparations have been diluted and modified with amino acids to make them more palatable for use as gargles for conditions like aphthous ulcers of the mouth. In veterinary medicine, aluminium triacetate's astringency property is used for treating Mortellaro disease in hoofed animals such as cattle.Aluminium triacetate is used as a mordant agent with dyes like alizarin, both alone and in combination. Together with aluminium diacetate or with aluminium sulfacetate it is used with cotton, other cellulose fibres, and silk. It has also been combined with ferrous acetate to produce different colours.

Carl Gräbe

Carl Gräbe (German: [ˈɡʁɛːbə]; 24 February 1841 – 19 January 1927) was a German industrial and academic chemist from Frankfurt am Main who held professorships in his field at Leipzig, Königsberg, and Geneva. He is known for the first synthesis of the economically important dye, alizarin, with Liebermann, and for contributing to the fundamental nomenclature of organic chemistry.

Carl Theodore Liebermann

Carl Theodore Liebermann (23 February 1842 – 28 December 1914) was a German chemist and student of Adolf von Baeyer.

Crimson

Crimson is a strong, red color, inclining to purple. It originally meant the color of the kermes dye produced from a scale insect, Kermes vermilio, but the name is now sometimes also used as a generic term for slightly bluish-red colors that are between red and rose.

List of dyes

This is a list of dyes with Colour Index International generic names and numbers.

Note

Synonyms should be treated with caution because they are often used inconsistently, see discussion page and external link [1]

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 1806, in the industry's adoption of industrial dyes, with the identification of alizarin in 1826, and in the emergence of modern medications, through the identification of codeine in 1832, a drug of widespread use with analgesic and antidiarrheal properties.

Robiquet was born in Rennes. He was at first a pharmacist in the French armies during the French Revolution years and became a professor at the École de pharmacie in Paris, where he died. (For biography details refer to the French Wikipedia article)

Notable scientific achievements were among other things his isolation and characterization of properties of asparagine (the first amino acid to be identified, from asparagus, achieved. In 1806, with Louis Nicolas Vauquelin), cantharidin (1810), the Sigma-1 receptor agonist noscapine (1817), caffeine (1821), alizarin (later on moved to mass industrial production by Carl Gräbe and Carl Theodore Liebermann in Germany, and by William Henry Perkin in Great Britain) and purpurin (1826), Orcin (1829), amygdalin (1830), as well as codeine (1832). Some of these discoveries were made in collaboration with other scientists.

Quinone

The quinones are a class of organic compounds that are formally "derived from aromatic compounds [such as benzene or naphthalene] by conversion of an even number of –CH= groups into –C(=O)– groups with any necessary rearrangement of double bonds", resulting in "a fully conjugated cyclic dione structure". The class includes some heterocyclic compounds.

The archetypical member of the class is 1,4-benzoquinone or cyclohexadienedione, often called simply "quinone" (thus the name of the class). Other important examples are 1,2-benzoquinone (ortho-quinone), 1,4-naphthoquinone and 9,10-anthraquinone.

Rose madder

Rose madder is the commercial name sometimes used to designate 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. As a paint, it has been described as "a fugitive, transparent, nonstaining, mid valued, moderately dull violet red pigment in tints and medum solutions, darkening to an impermanent, dull magenta red in masstone."

Rubia tinctorum

Rubia tinctorum, the common madder or dyer's madder, is a herbaceous perennial plant species belonging to the bedstraw and coffee family Rubiaceae.

Strawberry Thief (William Morris)

Strawberry Thief is one of William Morris's most popular repeating designs for textiles. It takes as its subject the thrushes that Morris found stealing fruit in his kitchen garden of his countryside home, Kelmscott Manor, in Oxfordshire. To print the pattern Morris used the painstaking indigo-discharge method he admired above all forms of printing. He first attempted to print by this method in 1875 but it was not until 1881, when he moved into his factory at Merton Abbey, near Wimbledon, that he succeeded. In May 1883 Morris wrote to his daughter, "I was a great deal at Merton last week ... anxiously superintending the first printing of the Strawberry thief, which I think we shall manage this time." Pleased with this success, he registered the design with the Patents Office. This pattern was the first design using the technique in which red (in this case alizarin dye;) and yellow (weld) were added to the basic blue and white ground.

The entire process would have taken days to complete and consequently, this was one of Morris & Co.'s most expensive cottons. Customers were not put off by the high price, however, and Strawberry Thief proved to be one of Morris's most commercially successful patterns. This printed cotton furnishing textile was intended to be used for curtains or draped around walls (a form of interior decoration advocated by William Morris), or for loose covers on furniture.

Wear Your Love Like Heaven

"Wear Your Love Like Heaven" is a song and US single by British singer-songwriter Donovan, released in 1967. It became the opening title of his 1967 double album A Gift from a Flower to a Garden. It reached chart position No. 23 in the USA.

The song mentions seven dye and pigment colours: Prussian blue, scarlet, crimson, Havana lake, carmine, rose carmethene and alizarin crimson.

Types of natural anthraquinones
Dihydroxyanthraquinones
Trihydroxyanthraquinones
Misc:

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