Crystal violet

Crystal violet
Kekulé, skeletal formula of a crystal violet minor tautomer
Ball-and-stick model of crystal violet as a chloride salt
Names
IUPAC name
Tris(4-(dimethylamino)phenyl)methylium chloride
Other names
  • Aniline violet
  • Basic violet 3
  • Baszol Violet 57L
  • Brilliant Violet 58
  • Hexamethyl-p-rosaniline chloride
  • Methylrosanilide chloride
  • Methyl Violet 10B
  • Methyl Violet 10BNS
  • Pyoktanin
Identifiers
548-62-9 YesY
1733-13-7 (base) N
3D model (Jmol) Interactive image
Interactive image
3580948
ChEBI CHEBI:41688 N
ChEMBL ChEMBL64894 YesY
ChemSpider 10588 YesY
DrugBank DB00406 N
ECHA InfoCard 100.034.892
EC Number 208-953-6
KEGG D01046 YesY
MeSH Gentian+violet
PubChem 11057
CID 68050 from PubChem (base)
RTECS number BO9000000
UNII J4Z741D6O5 YesY
B4JIJ2C6AT (base) N
UN number 3077
Properties
C25H30ClN3
Molar mass 407.99 g·mol−1
Melting point 205 °C (401 °F; 478 K)
Pharmacology
D01AE02 (WHO) G01AX09 (WHO)
Hazards
GHS pictograms
GHS signal word DANGER
H302, H318, H351, H410
P273, P280, P305+351+338, P501
Xn N
R-phrases R22, R40, R41, R50/53
S-phrases (S2), S26, S36/37/39, S46, S60, S61
Lethal dose or concentration (LD, LC):
1.2 g/kg (oral, mice)

1.0 g/kg (oral, rats)[1]

Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
N verify (what is YesYN ?)
Infobox references

Crystal violet or gentian violet (also known as methyl violet 10B or hexamethyl pararosaniline chloride) is a triarylmethane dye used as a histological stain and in Gram's method of classifying bacteria. Crystal violet has antibacterial, antifungal, and anthelmintic properties and was formerly important as a topical antiseptic. The medical use of the dye has been largely superseded by more modern drugs, although it is still listed by the World Health Organization.

The name "gentian violet" was originally used for a mixture of methyl pararosaniline dyes (methyl violet), but is now often considered a synonym for crystal violet. The name refers to its colour, being like that of the petals of a gentian flower; it is not made from gentians or from violets.

Production

A number of possible routes can be used to prepare crystal violet.[2][3] The original procedure developed by the German chemists Kern and Caro involved the reaction of dimethylaniline with phosgene to give 4,4′-bis(dimethylamino)benzophenone (Michler's ketone) as an intermediate.[4] This was then reacted with additional dimethylaniline in the presence of phosphorus oxychloride and hydrochloric acid.[5]

The dye can also be prepared by the condensation of formaldehyde and dimethylaniline to give a leuco dye:[2][3][6]

CH2O + 3 C6H5N(CH3)2 → CH(C6H4N(CH3)2)3 + H2O

Second, this colourless compound is oxidized to the coloured cationic form: (A typical oxidizing agent is manganese dioxide).

CH(C6H4N(CH3)2)3 + HCl +  1⁄2 O2 → [C(C6H4N(CH3)2)3]Cl + H2O

Dye colour

Crystal violet (pH indicator)
below pH −1.0 above pH 2.0
−1.0 ⇌ 2.0
Black lumps in a glass beaker
Solid crystal violet
Purple liquid in a test tube
Crystal violet in aqueous solution

When dissolved in water, the dye has a blue-violet colour with an absorbance maximum at 590 nm and an extinction coefficient of 87,000 M−1 cm−1.[7] The colour of the dye depends on the acidity of the solution. At a pH of 1.0, the dye is green with absorption maxima at 420 nm and 620 nm, while in a strongly acidic solution (pH of −1), the dye is yellow with an absorption maximum at 420 nm.

The different colours are a result of the different charged states of the dye molecule. In the yellow form, all three nitrogen atoms carry a positive charge, of which two are protonated, while the green colour corresponds to a form of the dye with two of the nitrogen atoms positively charged. At neutral pH, both extra protons are lost to the solution, leaving only one of the nitrogen atoms positive charged. The pKas for the loss of the two protons are approximately 1.15 and 1.8.[7]

In alkaline solutions, nucleophilic hydroxyl ions attack the electrophilic central carbon to produce the colourless triphenylmethanol or carbinol form of the dye. Some triphenylmethanol is also formed under very acidic conditions when the positive charges on the nitrogen atoms lead to an enhancement of the electrophilic character of the central carbon, which allows the nucleophilic attack by water molecules. This effect produces a slight fading of the yellow colour.

Applications

Nonmedical

Bacteria stained with crystal violet

Crystal violet is not used as a textile dye. Instead, it is used to dye paper and as a component of navy blue and black inks for printing, ball-point pens, and inkjet printers. It is also used to colourize diverse products such as fertilizers, antifreezes, detergents, and leather.

The dye is also used as a histological stain, particularly in Gram staining for classifying bacteria.

When conducting DNA gel electrophoresis, crystal violet can be used as a nontoxic DNA stain as an alternative to fluorescent, intercalating dyes such as ethidium bromide. Used in this manner, it may be either incorporated into the agarose gel or applied after the electrophoresis process is finished. Used at a 0.001% concentration and allowed to stain a gel after electrophoresis for 30 minutes, it can detect as little as 16ng of DNA. Through use of a methyl orange counterstain and a more complex staining method, sensitivity can be improved further to 8 ng of DNA.[8] When crystal violet is used as an alternative to fluorescent stains, it is not necessary to use ultraviolet illumination; this has made crystal violet popular as a means of avoiding UV-induced DNA destruction when performing DNA cloning in vitro.

In forensics, gentian violet was used to develop fingerprints. Crystal violet is also used as a tissue stain in the preparation of light microscopy sections.[9] In laboratory, solutions containing crystal violet and formalin are often used to simultaneously fix and stain cells grown in tissue culture to preserve them and make them easily visible, since most cells are colourless. It is also sometimes used as a cheap way to put identification markings on laboratory mice; since many strains of lab mice are albino, the purple colour stays on their fur for several weeks.

In body piercing, gentian violet is commonly used to mark the location for placing piercings, including surface piercings.

Medical

Tincture of Crystal violet used to Angular cheilitis on both corners of the mouth

Gentian violet has antibacterial, antifungal, antihelminthic, antitrypanosomal, antiangiogenic, and antitumor properties.[10][11]

It is used medically for these properties, in particular for dentistry, and is also known as "pyoctanin" (or "pyoctanine").[12] It is commonly used for:

In resource-limited settings, gentian violet is used to manage burn wounds,[13] inflammation of the umbilical cord stump (omphalitis) in the neonatal period,[14] oral candidiasis in HIV-infected patients[15] and mouth ulcers in children with measles.[16]

History

Crystal violet base (methylrosanilide, tris[4-(dimethylamino)phenyl]methanol, C25H31N3O)

Synthesis

Crystal violet is one of the components of methyl violet, a dye first synthesized by Charles Lauth in 1861.[17] From 1866, methyl violet was manufactured by the Saint-Denis-based firm of Poirrier et Chappat and marketed under the name "Violet de Paris". It was a mixture of the tetra-, penta- and hexamethylated pararosanilines.[18]

Crystal violet itself was first synthesized in 1883 by Alfred Kern (1850–1893) working in Basel at the firm of Bindschedler and Busch.[5] To optimize the difficult synthesis which used the toxic gas phosgene (carbonyl chloride), Kern entered into a collaboration with the German chemist Heinrich Caro at BASF.[4] Kern also found that by starting with diethylaniline rather than dimethylaniline, he could synthesize the closely related violet dye now known as C.I. 42600 or C.I. Basic violet 4.[19]

Gentian violet

The name "gentian violet" (or Gentianaviolett in German) is thought to have been introduced by the German pharmacist Georg Grübler, who in 1880 started a company in Leipzig that specialized in the sale of staining reagents for histology.[20][21] The gentian violet stain marketed by Grübler probably contained a mixture of methylated pararosaniline dyes.[22] The stain proved popular and in 1884 was used by Hans Christian Gram to stain bacteria. He credited Paul Ehrlich for the aniline-gentian violet mixture.[23] Grübler's gentian violet was probably very similar, if not identical, to Lauth's methyl violet, which had been used as a stain by Victor André Cornil in 1875.[24]

Although the name gentian violet continued to be used for the histological stain, the name was not used in the dye and textile industries.[25] The composition of the stain was not defined and different suppliers used different mixtures. In 1922, the Biological Stain Commission appointed a committee chaired by Harold Conn to look into the suitability of the different commercial products.[20] In his book Biological Stains, Conn describes gentian violet as a "poorly defined mixture of violet rosanilins".[25]

The German ophthalmologist Jakob Stilling is credited with discovering the antiseptic properties of gentian violet.[26] He published a monograph in 1890 on the bactericidal effects of a solution that he christened "pyoktanin", which was probably a mixture of aniline dyes similar to gentian violet.[27] He set up a collaboration with E. Merck & Co. to market "Pyoktanin caeruleum" as an antiseptic.

In 1902, Drigalski and Conradi found that although crystal violet inhibited the growth of many bacteria, it has little effect on Bacillus coli (Escherichia coli) and Bacillus typhi (Salmonella typhi), which are both Gram-negative bacteria.[28] A much more detailed study of the effects of Grübler's gentian violet on different strains of bacteria was published by John Churchman in 1912.[29] He found that most Gram-positive bacteria were sensitive to the dye, while most Gram-negative bacteria were not, and observed that the dye tended to act as a bacteriostatic agent rather than a bactericide.

Precautions

One study in mice demonstrated dose-related carcinogenic potential at several different organ sites.[30][31] The Food and Drug Administration in the US (FDA) has determined that gentian violet has not been shown by adequate scientific data to be safe for use in animal feed. Use of gentian violet in animal feed causes the feed to be adulterated and is a violation of the Federal Food, Drug, and Cosmetic Act in the US. On June 28, 2007, the FDA issued an "import alert" on farm raised seafood from China because unapproved antimicrobials, including gentian violet, had been consistently found in the products. The FDA report states:

"Like MG [malachite green], CV [crystal violet] is readily absorbed into fish tissue from water exposure and is reduced metabolically by fish to the leuco moiety, leucocrystal violet (LCV). Several studies by the National Toxicology Program reported that the carcinogenic and mutagenic effects of crystal violet in rodents. The leuco form induces renal, hepatic and lung tumor in mice."[32][33]

Gentian violet's common side effect is the staining of skin and cloth, but it can easily be washed off skin with a solution of bleach and water. However, if used on ulcerations or open wounds, it can cause tattooing. It is generally considered safe for use on children and breastfeeding mothers. It has even been applied to the mouth and lips of premature infants, and has a long history of safe use . Dr. Jack Newman recommends using gentian violet as a point on his "Candida Protocol", though limits the amount of time suggest for use by breastfeeding mothers.[34] La Leche League recommends gentian violet for thrush on the nipple.[35] However, in large quantities, gentian violet may lead to ulceration of a baby's mouth and throat and is linked with mouth cancer[36] and has been linked to cancer in the digestive tract of other animals.[37]

In Catch-22, the medics are portrayed as using gentian violet on feet and gums as a panacea. This may be because in World War I American soldiers returning after a leave were irrigated with gentian violet to prevent sexually transmitted disease.

In Picnic at Hanging Rock, the orphan Sara recounts how she was once punished by an orphanage's matron, who 'painted my head with gentian violet'.

Engineering students in Canada use gentian violet to dye their skin and jackets, a tradition started in honour of World War 2 Naval Engineers whose purple armbands would leave their skin dyed after countless days spent in the boiler rooms.

See also

References

  1. ↑ Hodge, H. C.; Indra, J.; Drobeck, H. P.; Duprey, L. P.; Tainter, M. L. (1972). "Acute oral toxicity of methylrosaniline chloride". Toxicology and Applied Pharmacology. 22 (1): 1–5. doi:10.1016/0041-008X(72)90219-0. PMID 5034986.
  2. 1 2 Colour Index 3rd Edition Volume 4 (PDF), Bradford: Society of Dyers and Colourists, 1971, p. 4391
  3. 1 2 Gessner, T.; Mayer, U. (2002), "Triarylmethane and Diarylmethane Dyes", Ullmann's Encyclopedia of Industrial Chemistry 6th Edition, Weinheim: Wiley-VCH, doi:10.1002/14356007.a27_179
  4. 1 2 Reinhardt, C.; Travis, A.S. (2000), Heinrich Caro and the creation of modern chemical industry, Dordrecht, Netherlands: Kluwer Academic, pp. 208–209, ISBN 0-7923-6602-6
  5. 1 2 US 290856, Caro, H. & A. Kern, "Manufacture of dye-stuff", issued 1883
    US 290891, Kern, A., "Manufacture of dye-stuff or coloring-matter", issued 1883
    US 290892, Kern, A., "Manufacture of purple dye-stuff", issued 1883
  6. ↑ Thetner, D. (2000), "Triphenylmethane and related dyes", Kirk-Othmer Encyclopedia of Chemical Technology, Wiley. Also available from Scribd.
  7. 1 2 Adams, E. Q.; Rosenstein, L. (1914). "The color and ionization of crystal-violet". J. Amer. Chem. Soc. 36 (7): 1452–1473. doi:10.1021/ja02184a014.
  8. ↑ Yang, Y.; Jung, D. W.; Bai, D. G.; Yoo, G. S.; Choi, J. K. (2001), "Counterion-dye staining method for DNA in agarose gels using crystal violet and methyl orange", Electrophoresis, 22 (5): 855–859, doi:10.1002/1522-2683()22:5<855::AID-ELPS855>3.0.CO;2-Y, PMID 11332752
  9. ↑ Henneman, Sheila A.; Kohn, Frank S. (1975), "Methylene blue staining of tissue culture monolayers", Methods in Cell Science, 1 (2): 103, doi:10.1007/BF01352624
  10. ↑ Docampo, R.; Moreno, S. N. (1990), "The metabolism and mode of action of gentian violet", Drug Metab. Rev., 22 (2–3): 161–178, doi:10.3109/03602539009041083, PMID 2272286
  11. ↑ Maley, Alexander M.; Arbiser, Jack L. (Dec 2013). "Gentian Violet: a 19th century drug re-emerges in the 21st century". Experimental Dermatology. 22 (12): 775–780. doi:10.1111/exd.12257. PMID 24118276.
  12. ↑ Gorgas, Ferdinand J. S. (1901), "Pyoctanin – Methyl-Violet – Pyoctanine", Dental Medicine. A Manual Of Dental Materia Medica And Therapeutics, 7th edition, chestofbooks.com, archived from the original on 2011-03-15, retrieved 2011-03-15.
  13. ↑ Choudhary, KN; Soni, PP; Sao, DK; Murthy, R; Deshkar, AM; Nanda, BR (April 2013). "Role of gentian violet paint in burn wound management: a prospective randomised control trial". J Indian Med Assoc. 111 (4): 248–50. PMID 24475556.
  14. ↑ Qamar, FN; Tikmani, SS; Mir, F; Zaidi, AK (Nov 2013). "Community-based management and outcome of omphalitis in newborns in Karachi, Pakistan.". JPMA. The Journal of the Pakistan Medical Association. 63 (11): 1364–9. PMID 24392520.
  15. ↑ Jurevic, RJ; Traboulsi, RS; Mukherjee, PK; Salata, RA; Ghannoum, MA; Oral HIV/AIDS Research Alliance Mycology Focus, group (May 2011). "Identification of gentian violet concentration that does not stain oral mucosa, possesses anti-candidal activity and is well tolerated.". European Journal of Clinical Microbiology & Infectious Diseases. 30 (5): 629–33. doi:10.1007/s10096-010-1131-8. PMC 3076549Freely accessible. PMID 21210170.
  16. ↑ Berman, Stephen; Nyquist, Christine; Lynch, Julia A.; Gentile, Ángela. Module 5. Management of Prevalent Infections in Children Following a Disaster (PDF). American Association of Pediatrics. p. 22. Retrieved 24 July 2014.
  17. ↑ Lauth, C. (1867), "On the new aniline dye, 'Violet de Paris'", Laboratory, 1: 138–139
  18. ↑ Gardner, W. M., ed. (1915), The British coal-tar industry : its origin, development, and decline, Philadelphia: Lippincott, p. 173
  19. ↑ US 290893, Kern, A., "Manufacture of dye-stuff or coloring-matter", issued 1883; Also available from Google.
  20. 1 2 Conn, H.J. (1922), "An investigation of American gentian violets: Report of Committee on Bacteriological Technic" (PDF), J. Bacteriol., 7 (5): 529–536
  21. ↑ Titford, M. (1993), "George Grübler and Karl Hollborn: two founders of the biological stain industry", J. Histotechnol., 16 (2): 155–158, doi:10.1179/his.1993.16.2.155, PMID 11615369
  22. ↑ Titford, M. (2007), "Comparison of historic Grübler dyes with modern counterparts using thin layer chromatography", Biotech. Histochem., 82 (4–5): 227–234, doi:10.1080/10520290701714005, PMID 18074269
  23. ↑ Clark, G.; Kasten, F.H. (1983), The history of staining (3rd ed.), Baltimore: Williams and Wilkins, pp. 95–97, ISBN 0-683-01705-5 (Earlier editions were authored by H.J. Conn)
  24. ↑ Cornil, V. (1875), "Sur la dissociation du violet de méthylaniline et sa séparation en deux couleurs sous l'influence de certains tissus normaux et pathologiques, en particulier par les tissus en dégénérescence amyloïde", Comptes Rendus de l'Académie des Sciences (in French), 80: 1288–1291
  25. 1 2 Conn, H.J. (1925), Biological stains: a handbook on the nature and uses of the dyes employed in the biological laboratory, Geneva, NY: Commission on Standardization of Biological Stains, pp. 68–69
  26. ↑ Council on Pharmacy and Chemistry (1937), New and Nonofficial Remedies, Chicago: American Medical Association, pp. 210–211
  27. ↑ Stilling, J. (1890), Anilin Farbstoffe als Antiseptica und ihre Anwendung in der Praxis (in German), Strassbourg: Mittheilung
  28. ↑ Drigalski, V.; Conradi, H. (1902), "Ueber ein Verfahren zum Nachweis der Typhusbacillen", Zeitschrift für Hygiene, 39 (1): 283–300, doi:10.1007/BF02140310
  29. ↑ Churchman, J.W. (1912), "The selective bactericidal action of gentian violet", Journal of Experimental Medicine, 16 (2): 221–247, plates 21–31, doi:10.1084/jem.16.2.221
  30. ↑ Littlefield, N.A.; Blackwell, B.N.; Hewitt, C.C.; Gaylor, D.W. (1985), "Chronic toxicity and carcinogenicity studies of gentian violet in mice", Fundam. Appl. Toxicol., 5 (5): 902–912, doi:10.1016/0272-0590(85)90172-1, PMID 4065463
  31. ↑ Carcinogenic Potency Database (CPDB)
  32. ↑ Questions and Answers on FDA's Import Alert on Farm-Raised Seafood From China: What evidence is there that malachite green, gentian violet and nitrofuran cause cancer?, US Food and Drug Administration, 2009, retrieved 2010-08-18
  33. ↑ How FDA Regulates Seafood (PDF), US Food and Drug Administration, 2007, retrieved 2014-10-27
  34. ↑ NBCIOnline. "Candida Protocol". www.nbci.ca. Retrieved 2016-09-15.
  35. ↑ www.lalecheleague.org
  36. ↑ Drinkwater, Paul (1990), "Gentian Violet — Is It Safe?", The Australian and New Zealand Journal of Obstetrics and Gynaecology, 30: 65, doi:10.1111/j.1479-828X.1990.tb03199.x.
  37. ↑ extoxnet.orst.edu

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