title: Selective derivatization of nucleotide diphosphate (NDP)-4-keto sugars for electrospray ionization-mass spectrometry (ESI-MS).
abstract: Nucleotide diphosphate (NDP) sugars are widely present in antibiotics and glycoconjugates, such as protein- and lipid-linked oligosaccharides, where they act as substrates for glycosyltransferase in eukaryotes and prokaryotes. Among NDP sugars, NDP-4-keto sugars are key intermediates in the synthesis of structurally diverse NDP sugars with different functional groups. However, the structural identification of the NDP-4-keto sugars via mass spectrometry (electrospray ionization-mass spectrometry (ESI-MS)) continues to be a challenge because of the carbonyl group in these sugars interferes with ionization process. In this study, we evaluated various hydroxylamine compounds for the derivatization of NDP-4-keto sugars, so that the detection of the sugars by ESI-MS is more efficient. As a result, O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine was found to be the most effective tagging molecule for the detection of NDP-4-keto sugars without being interfered by original MS. This method can be used for identifying NDP-4-keto sugars such as thymidine diphosphate (TDP)-, adenosine diphosphate (ADP)-, uridine diphosphate (UDP)-, and cytosine diphosphate (CDP)-4-keto sugars as well as new NDP-4-keto-dehydratases.
authors.affiliation: Department of Chemical Engineering, Soongsil University, Dongjak Gu156-743, Seoul, Republic of Korea.
authors.forename: Yun-Gon
authors.initials: YG
authors.lastname: Kim
authors.forename: Hyung-Yeon
authors.initials: HY
authors.lastname: Park
authors.forename: Dongwon
authors.initials: D
authors.lastname: Yoo
authors.forename: Changmin
authors.initials: C
authors.lastname: Sung
authors.forename: Eunjung
authors.initials: E
authors.lastname: Song
authors.forename: Jae-Hun
authors.initials: JH
authors.lastname: Lee
authors.forename: Yun-Hui
authors.initials: YH
authors.lastname: Choi
authors.forename: Yong-Hyun
authors.initials: YH
authors.lastname: Kim
authors.forename: Chang-Soo
authors.initials: CS
authors.lastname: Lee
authors.forename: Kyungmoon
authors.initials: K
authors.lastname: Park
authors.forename: Byung-Gee
authors.initials: BG
authors.lastname: Kim
authors.forename: Yung-Hun
authors.initials: YH
authors.lastname: Yang
mesh_terms: D006898:Hydroxylamines / Q000737:chemistry; D007661:Ketoses / Q000737:chemistry*; D009702:Nucleoside Diphosphate Sugars / Q000737:chemistry*; D021241:Spectrometry, Mass, Electrospray Ionization / Q000379:methods*; D005466:Fluorocarbons
chemical_list: D006898:Hydroxylamines; D007661:Ketoses; D009702:Nucleoside Diphosphate Sugars; C010277:Florox Reagent; D005466:Fluorocarbons