Sulfoluciferin is Biosynthesized by a Specialized Luciferin

May 26, 2016 - ... Cypridina luciferin sulfate, in the sea-firefly Cypridina (Vargula) hilgendorfii Tetrahedron 70, 2161– 2168 DOI: 10.1016/j.tet.20...
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Sulfoluciferin is Biosynthesized by a Specialized Luciferin Sulfotransferase in Fireflies Timothy R. Fallon,†,‡ Fu-Shuang Li,† Maria A. Vicent,†,§ and Jing-Ke Weng*,†,‡ †

Whitehead Institute for Biomedical Research, 9 Cambridge Center, Cambridge, Massachusetts 02142, United States Department of Biology, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, United States § Department of Biology, Williams College, Williamstown, Massachusetts 01267, United States ‡

Biochemistry 2016.55:3341-3344. Downloaded from pubs.acs.org by UNIV DE BARCELONA on 01/20/19. For personal use only.

S Supporting Information *

luciferin or to recycle the luminescent reaction product oxyluciferin.9,10 In an effort to elucidate firefly luciferin metabolism, we analyzed methanolic extracts of the posterior abdominal tissue containing the bioluminescent lantern (hereinafter referred to as “lantern” tissue) from the firefly Photinus pyralis by liquidchromatography high-resolution accurate-mass mass-spectrometry (LC-HRAM-MS). Under positive ion mode, this analysis detected luciferin as one of the most dominant mass features in the total ion chromatogram (TIC) (Figure S1). We also noted an identical ion to the luciferin [M + H]+ ion with a well resolved retention time 2 min earlier than that of luciferin (Figure S2). In-depth analysis of the MS1 and MS2 scans revealed that the luciferin-matching ion was likely an in-source fragment ion from a [M + H]+ precursor ion with a mass-tocharge ratio (m/z) of 360.9614. The 360.9614 precursor ion also had a highly similar fragmentation pattern to luciferin (Figure S3). Given the constraint of the luciferin chemical formula (C11H8N2O3S2) and the high mass accuracy (