Indigoidine

Indigoidine
Names
	Systematic IUPAC name (5E)-3-amino-5-(5-amino-2,6-dioxopyridin-3-ylidene)pyridine-2,6-dione
Identifiers
CAS Number	2435-59-8 ;
3D model (JSmol)	Interactive image;
ChEBI	CHEBI:79296;
ChemSpider	4590923;
PubChem CID	193349;
	InChI InChI=1S/C10H8N4O4/c11-5-1-3(7(15)13-9(5)17)4-2-6(12)10(18)14-8(4)16/h1-2,11H,12H2,(H,13,15,17)(H2,14,16,18) Key: YCZATMZTIWSFLZ-UHFFFAOYSA-N;
	SMILES C1=C(C(=O)NC(=O)C1=N)C2=C(NC(=O)C(=C2)N)O;
Properties
Chemical formula	C10H8N4O4
Molar mass	248,19 g·mol−1
Appearance	blue powder
	Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). Infobox references

Indigoidine is an organic compound of the azaquinone group. It is a blue pigment produced by some bacterial species that excrete it into the surrounding medium.

History

Otto Voges researched and described the bacterial species Bacillus indigoferus in 1893, renamed after him to Vogesella indigofera, in Kiel, which continuously discolored the surrounding medium (water) from slightly bluish (24 hours) to royal blue (48 hours).

In 1964 and 1965, Nobel laureate Richard Kuhn and his colleagues published several articles in the scientific press on the occurrence, structure and synthesis of indigoidine.^[2]^[3]^[4]

In 1979, Carl-Gerd Dieris and H.-D. Scharf described another synthesis of the compound.^[5]

Occurrence

Indigoidine occurs in the following species of bacteria:

Arthrobacter atrocyaneus
Arthrobacter crystallopoietes
Arthrobacter polychromogones
Corynebacterium insidiosum
Erwinia chrysanthemi renamed to Dickea dadantii
Vogesella indigofera previously Bacillus indigoferus and Pseudomonas indigofera

Synthesis

Indigoidine can be synthesized from citrazinic Acid (C₆H₅NO₄), which is itself produced from citric acid and ammonia.

Biosynthesis

The biosynthesis of indigoidine starts from glutamine, which is enzymatically oxidized, cyclized to the heterocycle and dimerized.^[6]

The names for the segments A, Ox, A, T and Te refer to defined domains within the enzyme structure of the bpsA gene product BPSA.^[7]

Properties

Physical properties

Indigoidine is a blue amorphous powder that is insoluble in water and most other solvents, but dissolves in hydrochloric acid, producing a royal blue color, and in hot sulfuric acid, producing an orange-brown color.^[8]

Chemical properties

The color of indigoidine is attributed to an indigoid chromophore. NMR spectroscopic studies of derivatives confirmed the stated symmetrical structure. Because of the nitrogen atoms in the quinoid rings, indigoidine is classified as azaquinones.

Derivatives

A derivative is the violet pigment N⁵,N^5′-Didodecylindigoidine, (C₃₄H₅₆N₄O₄), which was isolated from the psychrophile bacteria Shewanella violacea DSS12.^[9]

Literature

Carl-Gerd Dieris: Zur Frage der Luminiszenz von thermooxidativ geschädigten Polycarpolaktam. Eine neue Synthese des Bakterienfarbstoffes Indigoidin und seiner Tetra-N-alkylderivate. 1980.
Hans Günter Schlegel: Allgemeine Mikrobiologie. Thieme Verlagsgruppe, Stuttgart 1992, ISBN 978-3-13-444607-4.
Reverchon, Sylvie; Rouanet, Carine; Expert, Dominique; Nasser, William (2002-01-02). "Characterization of Indigoidine Biosynthetic Genes in Erwinia chrysanthemi and Role of This Blue Pigment in Pathogenicity". Journal of Bacteriology. 184 (3): 654–665. doi:10.1128/JB.184.3.654-665.2002. PMC 139515. PMID 11790734.
Christin Schönfeld: Charakterisierung und biochemische Analyse der Indigoidin Synthease BpsA aus S. lavendulae ATCC 11924. Masterarbeit, Philipps-Universität Marburg 2012.
M. Müller, S. Ausländer, D. Ausländer, C. Kemmer, M. Fussenegger: A novel reporter system for bacterial and mammalian cells based on the non-ribosomal peptide indigoidine. Metabolic Engineering 14/2012, S. 325–335 (doi:10.1016/j.ymben.2012.04.002).
H. Kobayashi, Y. Nogi, K. Hirokoshi: New violet 3,3'-bipyridyl pigment purified from deep-sea microorganism Shewanella violacea DSS12. In: Extremophiles Nr. 11(2)/2012, S. 245–250. PMID 17102923.

References

^ R. A. Abramovitch: The Chemistry of Heterocyclic Compounds. Pyridine and its Derivatives. John Wiley & Sons, New York 1974, ISBN 0-471-37915-8
^ Kuhn, Richard; Bauer, Helmut; Knackmuss, Hans-Joachim; Kuhn, Daisy A.; Starr, Mortimer P. (1964-01-01). "Die Struktur der blauen Pigmente von Corynebacterium insidiosum, Arthrobacter atrocyaneus, Pseudomonas indigofera und Arthrobacter crystallopoietes". Die Naturwissenschaften. 51 (17): 409. Bibcode:1964NW.....51..409K. doi:10.1007/BF00609040.
^ Kuhn, Richard; Bauer, Helmut; Knackmuss, Hans-Joachim (1965). "Struktur und Synthesen des Bakterienfarbstoffs Indigoidin". Chemische Berichte. 98 (7): 2139–2153. doi:10.1002/cber.19650980714. PMID 5849850.
^ Kuhn, Richard; Starr, Mortimer P.; Kuhn, Daisy A.; Bauer, Helmut; Knackmuss, Hans-Joachim (1965-03-01). "Indigoidine and other bacterial pigments related to 3,3'-bipyridyl". Archiv für Mikrobiologie. 51 (1): 71–84. Bibcode:1965ArMic..51...71K. doi:10.1007/BF00406851. PMID 14347925.
^ Dieris, C. -G.; Scharf, H. -D. (1979). "Eine neue Synthese des Bakterienfarbstoffs Indigoidin und seiner Tetra-N-alkyl-Derivate". Synthesis. 1979 (12): 948–950. doi:10.1055/s-1979-28883.
^ Müller, Marius; Ausländer, Simon; Ausländer, David; Kemmer, Christian; Fussenegger, Martin (2012). "A novel reporter system for bacterial and mammalian cells based on the non-ribosomal peptide indigoidine". Metabolic Engineering. 14 (4): 325–335. doi:10.1016/j.ymben.2012.04.002. PMID 22543310.
^ Takahashi, Hitoshi; Kumagai, Takanori; Kitani, Kyoko; Mori, Miwako; Matoba, Yasuyuki; Sugiyama, Masanori (2007). "Cloning and Characterization of a Streptomyces Single Module Type Non-ribosomal Peptide Synthetase Catalyzing a Blue Pigment Synthesis". Journal of Biological Chemistry. 282 (12). Elsevier BV: 9073–9081. doi:10.1074/jbc.m611319200. ISSN 0021-9258. PMID 17237222. Retrieved May 1, 2025.
^ Communications, EBCONT. "Indigoidin". RÖMPP, Thieme (in German). Retrieved May 1, 2025.
^ New violet 3,3'-bipyridyl pigment purified from deep-sea microorganism Shewanella violacea DSS12. 2007. pp. 245–250.

[1] R. A. Abramovitch: The Chemistry of Heterocyclic Compounds. Pyridine and its Derivatives. John Wiley & Sons, New York 1974, ISBN 0-471-37915-8

[2] Kuhn, Richard; Bauer, Helmut; Knackmuss, Hans-Joachim; Kuhn, Daisy A.; Starr, Mortimer P. (1964-01-01). "Die Struktur der blauen Pigmente von Corynebacterium insidiosum, Arthrobacter atrocyaneus, Pseudomonas indigofera und Arthrobacter crystallopoietes". Die Naturwissenschaften. 51 (17): 409. Bibcode:1964NW.....51..409K. doi:10.1007/BF00609040.

[3] Kuhn, Richard; Bauer, Helmut; Knackmuss, Hans-Joachim (1965). "Struktur und Synthesen des Bakterienfarbstoffs Indigoidin". Chemische Berichte. 98 (7): 2139–2153. doi:10.1002/cber.19650980714. PMID 5849850.

[4] Kuhn, Richard; Starr, Mortimer P.; Kuhn, Daisy A.; Bauer, Helmut; Knackmuss, Hans-Joachim (1965-03-01). "Indigoidine and other bacterial pigments related to 3,3'-bipyridyl". Archiv für Mikrobiologie. 51 (1): 71–84. Bibcode:1965ArMic..51...71K. doi:10.1007/BF00406851. PMID 14347925.

[5] Dieris, C. -G.; Scharf, H. -D. (1979). "Eine neue Synthese des Bakterienfarbstoffs Indigoidin und seiner Tetra-N-alkyl-Derivate". Synthesis. 1979 (12): 948–950. doi:10.1055/s-1979-28883.

[6] Müller, Marius; Ausländer, Simon; Ausländer, David; Kemmer, Christian; Fussenegger, Martin (2012). "A novel reporter system for bacterial and mammalian cells based on the non-ribosomal peptide indigoidine". Metabolic Engineering. 14 (4): 325–335. doi:10.1016/j.ymben.2012.04.002. PMID 22543310.

[7] Takahashi, Hitoshi; Kumagai, Takanori; Kitani, Kyoko; Mori, Miwako; Matoba, Yasuyuki; Sugiyama, Masanori (2007). "Cloning and Characterization of a Streptomyces Single Module Type Non-ribosomal Peptide Synthetase Catalyzing a Blue Pigment Synthesis". Journal of Biological Chemistry. 282 (12). Elsevier BV: 9073–9081. doi:10.1074/jbc.m611319200. ISSN 0021-9258. PMID 17237222. Retrieved May 1, 2025.

[8] Communications, EBCONT. "Indigoidin". RÖMPP, Thieme (in German). Retrieved May 1, 2025.

[9] New violet 3,3'-bipyridyl pigment purified from deep-sea microorganism Shewanella violacea DSS12. 2007. pp. 245–250.

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