One-pot non-enzymatic formation of firefly luciferin in a neutral buffer from p-benzoquinone and cysteine.
Firefly luciferin, the substrate for the bioluminescence reaction of luminous beetles, possesses a benzothiazole ring, which is rare in nature. Here, we demonstrate a novel one-pot reaction to give firefly luciferin in a neutral buffer from p-benzoquinone and cysteine without any synthetic reagents or enzymes. The formation of firefly luciferin was low in yield in various neutral buffers, whereas it was inhibited or completely prevented in acidic or basic buffers, in organic solvents, or under a nitrogen atmosphere. Labelling analysis of the firefly luciferin using stable isotopic cysteines showed that the benzothiazole ring was formed via the decarboxylation and carbon-sulfur bond rearrangement of cysteine. These findings imply that the biosynthesis of firefly luciferin can be developed/evolved from the non-enzymatic production of firefly luciferin using common primary biosynthetic units, p-benzoquinone and cysteine.
Graduate School of Bioagricultural Sciences, Nagoya University, Nagoya, 464-8601, Japan.
Shusei
S
Kanie
Graduate School of Bioagricultural Sciences, Nagoya University, Nagoya, 464-8601, Japan.
Toshio
T
Nishikawa
Graduate School of Bioagricultural Sciences, Nagoya University, Nagoya, 464-8601, Japan.
Makoto
M
Ojika
Graduate School of Bioagricultural Sciences, Nagoya University, Nagoya, 464-8601, Japan.|Department of Environmental Biology, College of Bioscience and Biotechnology, Chubu University, Kasugai 487-8501, Japan.
Yuichi
Y
Oba
D016227:Benzoquinones / Q000737:chemistry*; D002021:Buffers; D060326:Chemistry Techniques, Synthetic; D003545:Cysteine / Q000737:chemistry*; D003653:Decarboxylation; D049454:Firefly Luciferin / Q000737:chemistry*; D010100:Oxygen / Q000737:chemistry
D016227:Benzoquinones; D002021:Buffers; D049454:Firefly Luciferin; D003545:Cysteine; D010100:Oxygen