Vargulin

Vargulin
Names
IUPAC name
2-[3-[2-[(2S)-butan-2-yl]-6-(1H-indol-3-yl)-3-oxo-7H-imidazo[2, 1-c]pyrazin-8-yl]propyl]guanidine
Other names
  • Cypridina luciferin
  • Cypridinid luciferin
  • Vargula luciferin
Identifiers
3D model (JSmol)
ChemSpider
UNII
  • InChI=1S/C22H27N7O/c1-3-13(2)19-21(30)29-12-18(15-11-26-16-8-5-4-7-14(15)16)27-17(20(29)28-19)9-6-10-25-22(23)24/h4-5,7-8,11-13,26-27H,3,6,9-10H2,1-2H3,(H4,23,24,25) checkY
    Key: ZWPWSXGBDMGKKS-UHFFFAOYSA-N checkY
  • InChI=1S/C22H27N7O/c1-3-13(2)19-21(30)29-12-18(15-11-26-16-8-5-4-7-14(15)16)27-17(20(29)28-19)9-6-10-25-22(23)24/h4-5,7-8,11-13,26-27H,3,6,9-10H2,1-2H3,(H4,23,24,25)/t13-/m0/s1
    Key: ZWPWSXGBDMGKKS-UHFFFAOYAG
  • O=C\3N4\C=C(\c2c1ccccc1[nH]c2)N/C(=C4/N=C/3[C@@H](C)CC)CCC/N=C(\N)N
Properties
C22H27N7O
Molar mass 405.506 g·mol−1
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Vargulin, also called Cypridinid luciferin, Cypridina luciferin, or Vargula luciferin, is the luciferin found in the ostracod Cypridina hilgendorfii, also named Vargula hilgendorfii. These bottom dwelling ostracods emit a light stream into water when disturbed presumably to deter predation. Vargulin is also used by the midshipman fish, Porichthys.

History

A partial extraction procedure was developed in 1935 which involved reacting the compound with benzoyl chloride to allow it to be separated from the water-soluble components. The compound was first isolated and purified to crystals by Osamu Shimomura. The structure of the compound was confirmed some years later. Feeding experiments suggest that the compound is synthesized in the animal from three amino-acids: tryptophan, isoleucine, and arginine.

Biochemistry

Vargulin is oxidized by cypridina-luciferin 2-monooxygenase, a 62 kDa enzyme, to produce blue light at 462 nm (max emission, detected with a 425 to 525 nm filter).

2D representation of the chemical structure of vargulin .
vargulin
 
O2
CO2
Rightward reaction arrow with minor substrate(s) from top left and minor product(s) to top right
 
 
 
2D representation of the chemical structure of Q27102268.
oxidized vargulin
+ hν
 

The vargulin does not cross react with luciferases using coelenterazine or Firefly luciferin.

Uses

Vargulin (with the associated luciferase) has applications in biotechnology:

Although less stable, the Cypridina system is useful because can be used in multiplex assays with other (red-emitting) luciferin assays.

References

  1. ↑ Campbell AK, Herring PJ (1990). "Imidazolopyrazine bioluminescence in copepods and other marine organisms". Marine Biology. 104 (2). Springer Science and Business Media LLC: 219–225. Bibcode:1990MarBi.104..219C. doi:10.1007/bf01313261. ISSN 0025-3162. S2CID 84250053.
  2. ↑ Morin JG (2011). "Based on a review of the data, use of the term 'cypridinid' solves the Cypridina/Vargula dilemma for naming the constituents of the luminescent system of ostracods in the family Cypridinidae". Luminescence. 26 (1). Wiley: 1–4. doi:10.1002/bio.1282. ISSN 1522-7235. PMID 19862683.
  3. ↑ Shimomura, O. (2006). Bioluminescence: Chemical Principles and Methods. World Scientific Publishing. ISBN 978-981-256-801-4.
  4. ↑ Anderson, RS (1935). "Studies on Bioluminescence : II. the Partial Purification of Cypridina Luciferin". The Journal of General Physiology. 19 (2): 301–5. doi:10.1085/jgp.19.2.301. PMC 2141430. PMID 19872927.
  5. ↑ Shimomura, O, Goto, T, Hirata, Y (1957). "Crystalline Cypridina Luciferin". Bulletin of the Chemical Society of Japan. 30 (8): 929–933. doi:10.1246/bcsj.30.929. hdl:10069/20882.
  6. ↑ Kishi Y, Goto, T, Hirata Y, Shiromura O, Johnson FH (1966). "Cypridina bioluminescence. I. Structure of Cypridina luciferin". Tetrahedron Lett. 7 (29): 3427–3436. doi:10.1016/S0040-4039(01)82806-9.
  7. ↑ Oba, Y, Kato, S, Ojika, M, Inouye, S (2002). "Biosynthesis of luciferin in the sea firefly, Cypridina hilgendorfii: L-tryptophan is a component in Cypridina luciferin". Tetrahedron Letters. 43 (12): 2389–2392. doi:10.1016/S0040-4039(02)00257-5.
  8. ↑ Thompson EM, Nagata S, Tsuji FI (1989). "Cloning and expression of cDNA for the luciferase from the marine ostracod Vargula hilgendorfii". Proceedings of the National Academy of Sciences. 86 (17): 6567–71. Bibcode:1989PNAS...86.6567T. doi:10.1073/pnas.86.17.6567. PMC 297885. PMID 2771943.
  9. ↑ Karpetsky TP, White EH (1973). "The synthesis of Cypridina etioluciferamine and the proof of the structure of Cypridina luciferin". Tetrahedron. 29 (23): 3761–3773. doi:10.1016/0040-4020(73)80193-0.
  10. ↑ Tsuji FI, Lynch RV III, Stevens CL (1974). "Some properties of luciferase from the bioluminescent crustacean, Cypridina hilgendorfii". Biochemistry. 13 (25): 5204–5209. doi:10.1021/bi00722a024. PMID 4433517.
  11. ↑ "Luciferase Reporters". thermofisher.com.