title: Transformation of a wobble 2-thiouridine to 2-selenouridine via S-geranyl-2-thiouridine as a possible cellular pathway.
abstract: The newly discovered S-geranylated 2-thiouridines (geS2U) (Dumelin et al., 2012) and 2-selenouridines (Se2U) were recently shown to be synthesized by a single enzyme (selenouridine synthase, SelU) through two distinct pathways using the same 2-thiouridine substrate (S2U); however, no clear catalytic mechanism was proposed. We suggest that S-geranyl-2-thiouridine is an intermediate of the SelU-catalyzed conversion of S2U to Se2U. The successful chemical transformation of S2U→geS2U→Se2U is demonstrated here as an initial approximation of the intracellular pathway. The structure of Se2U was confirmed by spectroscopic methods, which included, for the first time, (77)Se NMR data (δ 354ppm).
authors: Institute of Organic Chemistry, Faculty of Chemistry, Lodz University of Technology, Zeromskiego 116, 90-924 Lodz, Poland. Electronic address: p.bartos@o2.pl.
authors: Paulina
authors: P
authors: Bartos
authors: Department of Bioorganic Chemistry, Centre of Molecular and Macromolecular Studies, Polish Academy of Sciences, Sienkiewicza 112, 90-363 Lodz, Poland. Electronic address: annamck@cbmm.lodz.pl.
authors: Anna
authors: A
authors: Maciaszek
authors: Department of Bioorganic Chemistry, Centre of Molecular and Macromolecular Studies, Polish Academy of Sciences, Sienkiewicza 112, 90-363 Lodz, Poland. Electronic address: arosinsk@cbmm.lodz.pl.
authors: Anna
authors: A
authors: Rosinska
authors: Institute of Organic Chemistry, Faculty of Chemistry, Lodz University of Technology, Zeromskiego 116, 90-924 Lodz, Poland. Electronic address: elzbieta.sochacka@p.lodz.pl.
authors: Elzbieta
authors: E
authors: Sochacka
authors: Department of Bioorganic Chemistry, Centre of Molecular and Macromolecular Studies, Polish Academy of Sciences, Sienkiewicza 112, 90-363 Lodz, Poland. Electronic address: bnawrot@cbmm.lodz.pl.
authors: Barbara
authors: B
authors: Nawrot
mesh_terms: D053898:Biosynthetic Pathways; D002477:Cells / Q000201:enzymology / Q000378:metabolism*; D015394:Molecular Structure; D016566:Organoselenium Compounds / Q000138:chemical synthesis* / Q000737:chemistry / Q000378:metabolism*; D013729:Terpenes / Q000737:chemistry* / Q000378:metabolism*; D013891:Thiouridine / Q000031:analogs & derivatives* / Q000737:chemistry / Q000378:metabolism; D014529:Uridine / Q000031:analogs & derivatives* / Q000138:chemical synthesis / Q000737:chemistry / Q000378:metabolism
chemical_list: C502847:2-selenouridine; C105273:2-thiouridine; D016566:Organoselenium Compounds; D013729:Terpenes; D013891:Thiouridine; D014529:Uridine
keywords: 2-Selenouridine; 2-Thiouridine; 77Se NMR; S-alkylation; S-geranyl-2-thiouridine; SelU; Selenium chemical shift; Selenouridine synthase