Selenium-enriched plants, such as hyperaccumulative phytoremediation plants (Astragalus praleongus, 517 micrograms g-1 Se, and Brassica juncea, 138 micrograms g-1 Se in dry sample), yeast (1200, 1922 and 2100, micrograms g-1 Se in dry sample), ramp (Allium tricoccum, 48, 77, 230, 252, 405 and 524 micrograms g-1 Se in dry sample), onion (Allium cepa, 96 and 140 micrograms g-1 Se in dry sample) and garlic (Allium sativum, 68, 112, 135, 296, 1355 micrograms g-1 Se in dry sample) were analyzed by HPLC-ICP-MS for their selenium content and speciation after hot water and enzymatic extractions. Reference samples with natural selenium levels, such as onion and garlic controls, cooking garlic powder, baking yeast powder and a commercial garlic supplement were also analyzed. Selected samples were also examined by HPLC-electrospray ionization (ESI)-MS. HPLC was mostly carried out with 0.1% heptafluorobutanoic acid (HFBA) as ion-pairing agent in 1 + 99 v/v methanol-water solution, but 0.1% trifluoroacetic acid (TFA) in 1 + 99 v/v methanol-water solution was also utilized to permit chromatography for compounds that did not elute with HFBA. More than 75% of the total eluting selenium compounds, based upon element specific detection, were identified from retention time data and standard spiking experiments, and between 60 and 85% of compounds were identified by MS, with up to 25% of the total eluting molecular selenium species being unidentified as yet. Limits of quantification (LOQ, defined as the concentration giving an S/N of 10) for HPLC-ICP-MS were in the range 2-50 ng mL-1 Se in the injected extracts for the selenium-enriched samples and 2-10 ng mL-1 Se for the natural selenium level samples. LOQ values for HPLC-ESI-MS were ca. 100 times higher than those measured by HPLC-ICP-MS.

A recent human intervention trial showed that daily supplementation with selenized yeast (Seyeast) led to a decrease in the overall cancer morbidity and mortality by nearly 50%; past research has also demonstrated that selenized garlic (Se-garlic) is very effective in mammary cancer chemoprevention in the rat model. The goal of this study was to compare certain biological activities of Se-garlic and Se-yeast and to elucidate the differences based on the chemical forms of selenium found in these two natural products. Characterization of organic selenium compounds in yeast (1922 µg/g Se) and garlic (296 µg/g Se) was carried out by high-performance liquid chromatography with inductively coupled plasma mass spectrometry or with electrospray mass spectrometry. Analytical speciation studies showed that the bulk of the selenium in Se-garlic and Se-yeast is in the form of γ-glutamyl-Se-methylselenocysteine (73%) and selenomethionine (85%), respectively. The above methodology has the sensitivity and capability to account for >90% of total selenium. In the rat feeding studies, supplementation of Se-garlic in the diet at different levels consistently caused a lower total tissue selenium accumulation when compared to Se-yeast. On the other hand, Se-garlic was significantly more effective in suppressing the development of premalignant lesions and the formation of adenocarcinomas in the mammary gland of carcinogen-treated rats. Given the present finding on the identity of selenomethionine and γ-glutamyl-Se-methylselenocysteine as the major form of selenium in Se-yeast and Se-garlic, respectively, the metabolism of these two compounds is discussed in an attempt to elucidate how their disposition in tissues might account for the differences in cancer chemopreventive activity.

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