The concerted application of element specific atomic spectral detection for chromatographic eluent monitoring allows previously unexploited qualitative and quantitative analytical concepts to be developed for the determination of selenium species. Selenium speciation is vital in order to better understand its metabolism and biological significance in clinical chemistry, biology, toxicology, and nutrition. Fluoroacid ion pair HPLC with ICP-MS detection and GC derivatization with atomic emission detection (AED) together aid analysis and elucidation of reaction pathways of selenium compounds in high selenium enriched yeast, as used widely in nutritional and clinical cancer preventative studies. Comparisons between currently produced and archived selenized yeasts show major differences in speciation. The formation of selenomethionine selenoxide and the identification of Se-S bonded S-(selenomethyl)-cysteine in archived nutritional yeast may be important for short and long term stability and nutritional activity studies.
Selenium-accumulating plants such as Brassica juncea (Indian mustard) concentrate the element in plant shoots and roots. Such behavior may provide a cost-effective technology to clean up contaminated soils and waters that pose major environmental and human health problems (phytoremediation). Such ability to transform selenium into bioactive compounds has important implications for human nutrition and health. Element selective characterization of B. juncea grown in the presence of inorganic selenium under hydroponic conditions provides valuable information to better understand selenium metabolism in plants. The present work determines both previously observed organoselenium species such as selenomethionine and Se-methylselenocysteine and for the first time detects the newly characterized S-(methylseleno)cysteine in plant shoots and roots when grown in the presence of selenate or selenite as the only selenium source. A key feature of this study is the complementary role of selenium and sulfur specific chromatographic detection by HPLC with interfaced inductively coupled plasma mass spectrometry (ICP-MS) detection and by derivatization GC with interfaced atomic spectral emission. HPLC-ICP-MS limits of detection for such species were in the range 5-50 ng Se mL −1 in the injected extracts. Speciation profiles are compared with those of selenium-enriched yeast by both HPLC-ICP-MS and GC-AED.
The complexity of selenium (Se) chemistry in the environment and in living organisms presents broad analytical challenges. The selective qualitative and quantitative determination of particular species of this element is vital in order to understand selenium's metabolism and significance in biology, toxicology, clinical chemistry and nutrition. This calls for state-of-the-art analytical techniques such as hyphenated methods that are reviewed with particular emphasis on interfaced separation with element-selective detection and identification of the detected selenium compounds. Atomic spectral element specific detection for monitoring chromatographic eluent enabled quantitative determination of selenium species in selenized yeast and qualitative measurement for breath samples. Gas chromatography with atomic emission detection (AED) of ethylated species and fluoroacid ion pair HPLC applied to the analysis of currently produced or archived selenized yeast and Brassica juncea have revealed the presence of a previously unrecognised Se-S amino acid, S-(methylseleno)cysteine.
After proteolytic digestion, aqueous extraction, and derivatization with diethyl pyrocarbonate or ethyl chloroformate, HPLC-inductively coupled plasma (ICP)-MS, GC-atomic emission detection (AED), and GC-MS analysis of high-selenium yeast stored at room temperature for more than 10 years showed selenomethionine as the major Se product along with substantial amounts of selenomethionine selenoxide hydrate and the previously unreported selenoamino acid having a Se-S bond, S-(methylseleno)cysteine. The identity of the latter compound was confirmed by synthesis. The natural product was shown to be different from a synthetic sample of the isomeric compound Se-(methylthio)selenocysteine. Selenium-specific NMR spectroscopic methods were developed to directly analyze the aqueous extracts of the hydrolyzed selenized yeast without derivatization or separation. Selenomethionine and S-(methylseleno)cysteine were identified by 77 Se-1 H HMQC-TOCSY experiments.
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