Firefly luciferin

Firefly luciferin
Names
IUPAC name
(4S)-2-(6-hydroxy-1,3-benzothiazol-2-yl)-4,5-dihydrothiazole-4-carboxylic acid
Other names
D-(−)-Luciferin
Identifiers
2591-17-5
ChemSpider 4588411
16735812 One of the other tautomeric representations
Jmol-3D images Image
PubChem 5484207
Properties
Molecular formula
 C11H8N2O3S2
Molar mass 280.32 g·mol−1
Except where noted otherwise, data is given for materials in their standard state (at 25 °C (77 °F), 100 kPa)
Infobox references

Firefly luciferin is the luciferin, or light-emitting compound, found in many firefly (Lampyridae) species. It is the substrate of luciferase (EC 1.13.12.7), which is responsible for the characteristic yellow light emission from many firefly species.

As with all other luciferins, oxygen is required to elicit light; however, it has also been found that adenosine triphosphate (ATP) and magnesium are required for light emission.[1][2]

History

Much of the early work on the chemistry of the firefly luminescence was done in the lab of William D. McElroy at Johns Hopkins University. The luciferin was first isolated and purified in 1949, though it would be several years until a procedure was developed to crystallize the compound in high yield. This, along with the synthesis and structure elucidation, was accomplished by Dr. Emil H. White at the Johns Hopkins University, Department of Chemistry.[3] The procedure was an acid-base extraction, given the carboxylic acid group on the luciferin. The luciferin could be effectively extracted using ethyl acetate at low pH from powder of approximately 15,000 firefly lanterns.[4] The structure was later confirmed by combined use of infrared spectroscopy, UV-vis spectroscopy and synthetic methods to degrade the compound into identifiable fragments.[5]

Properties

Crystal luciferin was found to be fluorescent, absorbing ultraviolet light with a peak at 327 nm and emitting light with a peak at 530 nm. Alkaline solutions caused a redshift of the absorption likely due to deprotonation of the hydroxyl group on the benzothiazole, but did not affect the fluorescence emission. It was found that the luciferyl adenylate (the AMP ester of luciferin) spontaneously emits light in solution.[6] Different species of fireflies all use the same luciferin, however the color of the light emitted can differ greatly. The light from Photuris pennsylvanica was measured to be 552 nm (green-yellow) while Pyrophorus plagiophthalamus was measured to emit light at 582 nm (orange) in the ventral organ. Such differences are likely due to pH changes or differences in primary structure of the luciferase.[7]

Biological Activity

The in vivo synthesis of firefly luciferin is not completely understood. Only the final step of the enzymatic pathway has been studied, which is the condensation reaction of D-cysteine with 2-cyano-6-hydroxybenzothiazole, and is the same reaction used to produce the compound synthetically.[8] This was confirmed by radiolabeling of atoms in the two compounds and by identification of a luciferin-regenerating enzyme.[9]

In firefly, oxidation of luciferins, which is catalyzed by luciferases, yields a peroxy compound 1,2-dioxetane. The dioxetane is unstable and decays spontaneously to carbon dioxide and excited ketones, which release excess energy by emitting light (bioluminescence).[10]

Loss of CO2 of a dioxetane, giving rise to an excited ketone, which relaxes by emitting light.

References

  1. ↑ McElroy WD (1947). "The Energy Source for Bioluminescence in an Isolated System.". Proc Natl Acad Sci USA 33 (11): 342–345. doi:10.1073/pnas.33.11.342. PMC 1079070. PMID 16588763.
  2. ↑ Green A, McElroy WD (1956). "Function of adenosine triphosphate in the activation of luciferin.". Arch Biochem Biophys 64 (2): 257–271. doi:10.1016/0003-9861(56)90268-5. PMID 13363432.
  3. ↑ Strehler BL, McElroy WD (1949). "Purification of firefly luciferin.". J Cell Physiol 34 (3): 457–466. doi:10.1002/jcp.1030340310. PMID 15406363.
  4. ↑ Bitler B, McElroy WD (1957). "The Preparation and Properties of Crystalline Firely Luciferin". Arch Biochem Biophys 72 (2): 358–368. doi:10.1016/0003-9861(57)90212-6. PMID 13479120.
  5. ↑ White EH, McCapra F, Field GF, and McElroy WD (1961). "The Structure and Synthesis of Firefly Luciferin". J Am Chem Soc 83 (10): 2402–2403. doi:10.1021/ja01471a051.
  6. ↑ Rhodes WC, McElroy WD (1958). "The synthesis and function of luciferyl-adenylate and oxyluciferyl-adenylate.". J Biol Chem 233 (6): 1528–1537. PMID 13610868.
  7. ↑ Seliger HH, Buck JB, Fastie WG, McElroy WD (1964). "The Spectral Distribution of Firefly Light.". J Gen Physiol 48 (1): 95–104. doi:10.1085/jgp.48.1.95. PMC 2195396. PMID 14212153.
  8. ↑ White EH, Worther H, Field GF, and McElroy WD (1965). "Analogs of Firefly Luciferin.". J. Org. Chem. 30 (7): 2344–2348. doi:10.1021/jo01018a054.
  9. ↑ Gomi K, Kajiyama N (2001). "Oxyluciferin, a Luminescence Product of Firefly Luciferase, Is Enzymatically Regenerated into Luciferin.". J Biol Chem 276 (39): 36508–36513. doi:10.1074/jbc.M105528200. PMID 11457857.
  10. ↑ Aldo Roda Chemiluminescence and Bioluminescence: Past, Present and Future, p. 57, Royal Society of Chemistry, 2010, ISBN 1-84755-812-7

External links