Firefly luciferin

Short description: Chemical compound

Firefly luciferin

Names
IUPAC name

(4S)-2-(6-hydroxy-1,3-benzothiazol-2-yl)-4,5-dihydrothiazole-4-carboxylic acid

Other names

D-(−)-Luciferin, beetle luciferin

Identifiers

CAS Number

* 2591-17-5

3D model (JSmol)

* Interactive image

ChemSpider |

* 4588411
* 16735812 One of the other tautomeric representations

EC Number |

* 219-981-3

PubChem CID

* 92934

UNII |

* 5TBB02N29K

InChI

* InChI=1S/C11H8N2O3S2/c14-5-1-2-6-8(3-5)18-10(12-6)9-13-7(4-17-9)11(15)16/h1-3,7,14H,4H2,(H,15,16)/t7-/m1/s1

Key: BJGNCJDXODQBOB-SSDOTTSWSA-N

* One of the other tautomeric representations: InChI=1S/C11H8N2O3S2/c14-5-1-2-6-8(3-5)18-10(12-6)9-13-7(4-17-9)11(15)16/h1-3,7,13H,4H2,(H,15,16)/b10-9+/t7-/m1/s1

* InChI=1S/C11H8N2O3S2/c14-5-1-2-6-8(3-5)18-10(12-6)9-13-7(4-17-9)11(15)16/h1-3,7,14H,4H2,(H,15,16)/t7-/m1/s1

SMILES

* O=C(O)[C@@H]1/N=C(\SC1)c2sc3cc(O)ccc3n2

Properties

Chemical formula

| C11H8N2O3S2
Molar mass | 280.32 g·mol−1
Appearance  | Yellow Powder [1]
UV-vis (λmax)  | 330 nm (neutral and somewhat acidic aqueous solutions) [2]
Absorbance | ε330 = 18.2 mM−1 cm−1[2]
Hazards
GHS pictograms |
GHS Signal word | Warning

GHS hazard statements

| H315, H319, H335

GHS precautionary statements

| P261, P264, P271, P280, P302+352, P304+340, P305+351+338, P312, P321, P332+313, P337+313, P362, P403+233, P405, P501

Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Infobox references

Tracking categories (test):

* SizeSet

Firefly luciferin (also known as beetle luciferin) is the luciferin, precursor of the light-emitting compound, used for the firefly (Lampyridae), railroad worm (Phengodidae), starworm (Rhagophthalmidae), and click-beetle (Pyrophorini) bioluminescent systems.[1] It is the substrate of firefly luciferase (EC 1.13.12.7), which is responsible for the characteristic light emission of many firefly and other insect species in the visible spectra ranging from 530 until 630 nm.[3]

As with other luciferins, oxygen is essential for the luminescence mechanism, which involves the decomposition of a cyclic peroxide to produce excited-state molecules capable of emitting light as they relax to the ground state.[1] Additionally, it has been found that adenosine triphosphate (ATP) and magnesium are required for light emission.[4][5]

## Contents

* 1 History
* 2 Properties
* 3 Biological activity
* 4 References
* 5 External links

## 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 from a large amount of specimens, 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.[6] 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.[7] The structure was later confirmed by combined use of infrared spectroscopy, UV–vis spectroscopy and synthetic methods to degrade the compound into identifiable fragments.[8]

## 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. Visible emission occurs upon relaxation of the oxyluciferin from a singlet excited state down to its ground state.[9] 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.[10] 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.[11] Modification of the firefly luciferin substrate has led to "red-shifted" emissions (up to emission wavelength of 675 nm).[12]

## 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.[13] This was confirmed by radiolabeling of atoms in the two compounds and by identification of a luciferin-regenerating enzyme.[14]

In firefly, oxidation of luciferins, which is catalyzed by luciferases, yields a peroxy compound 1,2-dioxetanone.[1] The dioxetanone is unstable and via the release of carbon dioxide and excited ketones, which release excess energy by emitting light (bioluminescence).[15]

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

The overall reaction is:[1]

Template:Chemrxn

Firefly luciferin and modified substrates are fatty acid mimics and have been used to localize fatty acid amide hydrolase (FAAH) in vivo.[16] Firefly luciferin is a substrate of the ABCG2 transporter and has been used as part of a bioluminescence imaging high throughput assay to screen for inhibitors of the transporter.[17]

## References

1. ↑ 1.0 1.1 1.2 1.3 1.4 Schramm, Stefan; Weiß, Dieter (2024). "Bioluminescence – The Vibrant Glow of Nature and its Chemical Mechanisms" (in en). ChemBioChem 25 (9). doi:10.1002/cbic.202400106. ISSN 1439-7633. PMID 38469601.
2. ↑ 2.0 2.1 "D-luciferin product information". Sigma Aldrich. https://www.sigmaaldrich.com/content/dam/sigma-aldrich/docs/Sigma/Product_Information_Sheet/2/l9504pis.pdf.
3. ↑ Carrasco-López, César; Lui, Nathan M.; Schramm, Stefan; Naumov, Panče (2021). "The elusive relationship between structure and colour emission in beetle luciferases" (in en). Nature Reviews Chemistry 5 (1): 4–20. doi:10.1038/s41570-020-00238-1. ISSN 2397-3358. PMID 37118106. https://www.nature.com/articles/s41570-020-00238-1.
4. ↑ 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. PMID 16588763. Bibcode: 1947PNAS...33..342M.
5. ↑ "Function of adenosine triphosphate in the activation of luciferin.". Arch Biochem Biophys 64 (2): 257–271. 1956. doi:10.1016/0003-9861(56)90268-5. PMID 13363432.
6. ↑ "Purification of firefly luciferin.". J Cell Physiol 34 (3): 457–466. 1949. doi:10.1002/jcp.1030340310. PMID 15406363.
7. ↑ "The Preparation and Properties of Crystalline Firely Luciferin". Arch Biochem Biophys 72 (2): 358–368. 1957. doi:10.1016/0003-9861(57)90212-6. PMID 13479120.
8. ↑ "The Structure and Synthesis of Firefly Luciferin". J Am Chem Soc 83 (10): 2402–2403. 1961. doi:10.1021/ja01471a051. Bibcode: 1961JAChS..83.2402W.
9. ↑ "Firefly Bioluminescence: A Mechanistic Approach of Luciferase Catalyzed Reactions". IUBMB Life 61 (1): 6–17. 2009. doi:10.1002/iub.134. PMID 18949818.
10. ↑ "The synthesis and function of luciferyl-adenylate and oxyluciferyl-adenylate.". J Biol Chem 233 (6): 1528–1537. 1958. doi:10.1016/S0021-9258(18)49367-2. PMID 13610868.
11. ↑ "The Spectral Distribution of Firefly Light.". J Gen Physiol 48 (1): 95–104. 1964. doi:10.1085/jgp.48.1.95. PMID 14212153.
12. ↑ "Multicolor Bioluminescence Obtained Using Firefly Luciferin". Current Topics in Medicinal Chemistry 16 (24): 2648–2655. 2016. doi:10.2174/1568026616666160413135055. PMID 27072707.
13. ↑ "Analogs of Firefly Luciferin.". J. Org. Chem. 30 (7): 2344–2348. 1965. doi:10.1021/jo01018a054.
14. ↑ "Oxyluciferin, a Luminescence Product of Firefly Luciferase, Is Enzymatically Regenerated into Luciferin.". J Biol Chem 276 (39): 36508–36513. 2001. doi:10.1074/jbc.M105528200. PMID 11457857.
15. ↑ Aldo Roda Chemiluminescence and Bioluminescence: Past, Present and Future, p. 57, Royal Society of Chemistry, 2010, ISBN 1-84755-812-7
16. ↑ "Luciferin Amides Enable in Vivo Bioluminescence Detection of Endogenous Fatty Acid Amide Hydrolase Activity". J. Am. Chem. Soc. 137 (27): 8684–8687. 2015. doi:10.1021/jacs.5b04357. PMID 26120870. Bibcode: 2015JAChS.137.8684M.
17. ↑ "Identification of Inhibitors of ABCG2 by a Bioluminescence Imaging-Based High-Throughput Assay.". Cancer Res. 69.

## External links

* Bioluminescence Page showing major luciferin types

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*[CID]: Compound ID
*[H315]: Causes skin irritation
*[H319]: Causes serious eye irritation
*[H335]: May cause respiratory irritation
*[P261]: Avoid breathing dust/fume/gas/mist/vapours/spray
*[P264]: Wash … thoroughly after handling
*[P271]: Use only outdoors or in a well-ventilated area
*[P280]: Wear protective gloves/protective clothing/eye protection/face protection
*[P302+352]: IF ON SKIN: Wash with soap and water
*[P304+340]: IF INHALED: Remove victim to fresh air and keep at rest in a position comfortable for breathing
*[P305+351+338]: IF IN EYES: Rinse continuously with water for several minutes. Remove contact lenses if present and easy to do – continue rinsing
*[P312]: Call a POISON CENTER or doctor/physician if you feel unwell
*[P321]: Specific treatment (see … on this label)
*[P332+313]: If skin irritation occurs: Get medical advice/attention
*[P337+313]: Get medical advice/attention
*[P362]: Take off contaminated clothing and wash before reuse
*[P403+233]: Store in a well ventilated place. Keep container tightly closed
*[P405]: Store locked up
*[P501]: Dispose of contents/container to …