title: Liquid chromatography-mass spectrometry (LC-MS): a powerful combination for selenium speciation in garlic (Allium sativum).
abstract: Liquid chromatography (LC) hyphenated with both elemental and molecular mass spectrometry has been used for Se speciation in Se-enriched garlic. Different species were separated by ion-pair liquid chromatography-inductively coupled plasma mass spectrometry (LC-ICP-MS) after hot-water extraction. They were identified by on-line reversed-phase liquid chromatography-electrospray ionization tandem mass spectrometry (RPLC-ESI-MS-MS). Se-methionine and Se-methylselenocysteine were determined by monitoring their product ions. Another compound, gamma-glutamyl-Se-methylselenocysteine, shown to be the most abundant form of Se in the garlic, was determined without any additional sample pre-treatment after extraction and without the need for a synthesized standard. Product ions for this dipeptide were detected by LC-ESI-MS-MS for three isotopes of Se-78 Se, 80Se: and 82Se. The method was extended to the species extracted during in-vitro gastrointestinal digestion. Because both Se-methylselenocysteine and gamma-glutamyl-Se-methylselenocysteine have anticarcinogenic properties, their extractability and stability during human digestion are very important. Garlic was also treated with saliva, to enable detection and analysis of species extracted during mastication. Detailed information on the extractability of selenium species by both simulated gastric and intestinal fluid are given, and variation of the distribution of Se among the different species with time is discussed. Although the main species in garlic is the dipeptide gamma-glutamyl-Se-methylselenocysteine, Se-methylselenocysteine is the main compound present in the extracts after treatment with gastrointestinal fluids. Two more, so far unknown compounds were observed in the chromatogram. The extracted species and their transformations were analysed by combining LC-ICP-MS and LC-ESI-MS-MS. In both the simulated gastric and intestinal digests, Se-methionine, Se-methylselenocysteine, and gamma-glutamyl-Se-methylselenocysteine could be determined by LC-ESI-MS-MS by measuring their typical product ions.
authors.affiliation: Department of Analytical Chemistry, Ghent University, UGent, Proeftuinstraat 86, 9000 Gent, Belgium. emmie.dumont@ugent.be
authors.forename: Emmie
authors.initials: E
authors.lastname: Dumont
authors.forename: Yasumitsu
authors.initials: Y
authors.lastname: Ogra
authors.forename: Frank
authors.initials: F
authors.lastname: Vanhaecke
authors.forename: Kazuo T
authors.initials: KT
authors.lastname: Suzuki
authors.forename: Rita
authors.initials: R
authors.lastname: Cornelis
mesh_terms: D002853:Chromatography, Liquid / Q000295:instrumentation / Q000379:methods; D005737:Garlic / Q000737:chemistry*; D013058:Mass Spectrometry / Q000295:instrumentation / Q000379:methods*; D016566:Organoselenium Compounds / Q000032:analysis*; D012643:Selenium / Q000032:analysis*; D012680:Sensitivity and Specificity; D013997:Time Factors
chemical_list: D016566:Organoselenium Compounds; D012643:Selenium