Selenium Species in Aqueous Extracts of Alfalfa Sprouts by Two-Dimensional Liquid Chromatography Coupled to Inductively Coupled Plasma Mass Spectrometry and Electrospray Mass Spectrometry Detection
The complementary use of two different liquid chromatographic mechanisms coupled to inductively coupled plasma mass spectrometry (ICP-MS) for selenium (Se) specific detection has permitted the screening of the most abundant Se-containing fractions in selenized alfalfa sprouts (Medicago sativa). Aqueous extracts of the sprouts were fractionated first by size exclusion chromatography (SEC) using a Superdex Peptide column and a mobile phase containing an ammonium acetate buffer (pH 7). Further purification of the individual SEC Se-containing fractions was carried out using two different chromatographic systems: a Shodex Ashaipack column, with a mixed mechanism of size exclusion and ion exchange, and a conventional reversed phase C8 using ion-pairing reagents. In both cases, the columns were coupled to an inductively coupled plasma mass spectrometer equipped with an octapole reaction system for Se specific detection. This system allowed the on-line monitoring of the most abundant Se isotopes (78Se, 80Se) by reducing the possible polytomic interferences affecting these ions by adding hydrogen (2 mL min-1) to the octapole reaction cell. The results obtained by both separation mechanisms were highly comparable, revealing the presence of Se-methionine and Se-methyl selenocysteine. Both compounds were then confirmed by analyzing the corresponding fractions by electrospray quadrupole-time-of-flight (ESI-Q-TOF) mass spectrometry. Finally, an additional Se-containing species showing Se isotope distribution was detected at a molecular ion m/z 239 in the ESI-Q-TOF. The collision-induced dissociation of the m/z 239 and 237 ions (corresponding to 80Se and 78Se isotopes, respectively) revealed the possible presence as well of a derivative of the Se-2-propenyl selenocysteine.
Keywords: Selenium; alfalfa sprouts; HPLC-ICP-MS; ESI-Q-TOF
University of Oviedo.
Corvinus University of Budapest.
To whom correspondence should be addressed.
This article is cited by 21 publications.
- Mihaly Dernovics and Ryszard Lobinski . Speciation Analysis of Selenium Metabolites in Yeast-Based Food Supplements by ICPMS—Assisted Hydrophilic Interaction HPLC—Hybrid Linear Ion Trap/Orbitrap MSn. Analytical Chemistry 2008, 80 (11) , 3975-3984. https://doi.org/10.1021/ac8002038
- Adriana Alzate, Benito Cañas, Sandra Pérez-Munguía, Hector Hernández-Mendoza, Concepción Pérez-Conde, Ana Maria Gutiérrez and Carmen Cámara . Evaluation of the Inorganic Selenium Biotransformation in Selenium-Enriched Yogurt by HPLC-ICP-MS. Journal of Agricultural and Food Chemistry 2007, 55 (24) , 9776-9783. https://doi.org/10.1021/jf071596d
- Sahar Ehsani, David James, Zahra Molaie Oskouie. Determining selenium speciation by graphite furnace atomic absorption spectrometry. Environmental Monitoring and Assessment 2021, 193 (9) https://doi.org/10.1007/s10661-021-09375-6
- Hammad Ullah, Rifat Ullah Khan, Vincenzo Tufarelli, Vito Laudadio. Selenium: An Essential Micronutrient for Sustainable Dairy Cows Production. Sustainability 2020, 12 (24) , 10693. https://doi.org/10.3390/su122410693
- Anna Ruszczyńska, Anna Konopka, Eliza Kurek, Julio Cesar Torres Elguera, Ewa Bulska. Investigation of biotransformation of selenium in plants using spectrometric methods. Spectrochimica Acta Part B: Atomic Spectroscopy 2017, 130 , 7-16. https://doi.org/10.1016/j.sab.2017.02.004
- Rajani Jagtap, William Maher, Frank Krikowa, Michael J. Ellwood, Simon Foster. Measurement of selenomethionine and selenocysteine in fish tissues using HPLC-ICP-MS. Microchemical Journal 2016, 128 , 248-257. https://doi.org/10.1016/j.microc.2016.04.021
- Malgorzata Bodnar, Marzena Szczyglowska, Piotr Konieczka, Jacek Namiesnik. Methods of Selenium Supplementation: Bioavailability and Determination of Selenium Compounds. Critical Reviews in Food Science and Nutrition 2016, 56 (1) , 36-55. https://doi.org/10.1080/10408398.2012.709550
- Rajani Jagtap, William Maher. Determination of selenium species in biota with an emphasis on animal tissues by HPLC–ICP-MS. Microchemical Journal 2016, 124 , 422-529. https://doi.org/10.1016/j.microc.2015.07.014
- C.G. Vogiatzis, G.A. Zachariadis. Tandem mass spectrometry in metallomics and the involving role of ICP-MS detection: A review. Analytica Chimica Acta 2014, 819 , 1-14. https://doi.org/10.1016/j.aca.2014.01.029
- Virginia Funes-Collado, Albert Morell-Garcia, Roser Rubio, José Fermín López-Sánchez. Study of selenocompounds from selenium-enriched culture of edible sprouts. Food Chemistry 2013, 141 (4) , 3738-3743. https://doi.org/10.1016/j.foodchem.2013.06.090
- MALGORZATA BODNAR, PIOTR KONIECZKA, JACEK NAMIESNIK. The Properties, Functions, and Use of Selenium Compounds in Living Organisms. Journal of Environmental Science and Health, Part C 2012, 30 (3) , 225-252. https://doi.org/10.1080/10590501.2012.705164
- Søren Husted, Daniel P. Persson, Kristian H. Laursen, Thomas H. Hansen, Pai Pedas, Michaela Schiller, Josefine N. Hegelund, Jan K. Schjoerring. Review: The role of atomic spectrometry in plant science. J. Anal. At. Spectrom. 2011, 26 (1) , 52-79. https://doi.org/10.1039/C0JA00058B
- Nahid Mashkouri Najafi, Shahram Seidi, Reza Alizadeh, Hamed Tavakoli. Inorganic selenium speciation in environmental samples using selective electrodeposition coupled with electrothermal atomic absorption spectrometry. Spectrochimica Acta Part B: Atomic Spectroscopy 2010, 65 (4) , 334-339. https://doi.org/10.1016/j.sab.2010.02.017
- Yasumitsu Ogra, Yasumi Anan. Selenometabolomics: Identification of selenometabolites and specification of their biological significance by complementary use of elemental and molecular mass spectrometry. Journal of Analytical Atomic Spectrometry 2009, 24 (11) , 1477. https://doi.org/10.1039/b910235c
- Teresa Cecchi. Ion Pairing Chromatography. Critical Reviews in Analytical Chemistry 2008, 38 (3) , 161-213. https://doi.org/10.1080/10408340802038882
- Owen T. Butler, Jennifer M. Cook, Chris F. Harrington, Steve J. Hill, John Rieuwerts, Douglas L. Miles. Atomic spectrometry update. Environmental analysis. Journal of Analytical Atomic Spectrometry 2008, 23 (2) , 249. https://doi.org/10.1039/b718954k
- Teresa Cecchi. Application of Ion Pairing Chromatography to the Analysis of Inorganic Analytes: Review. Journal of Liquid Chromatography & Related Technologies 2007, 30 (9-10) , 1205-1225. https://doi.org/10.1080/10826070701274379
- . Current literature in mass spectrometry. Journal of Mass Spectrometry 2007, 266-277. https://doi.org/10.1002/jms.1071
- Yasumitsu Ogra, Takashi Kitaguchi, Kazuya Ishiwata, Noriyuki Suzuki, Yuji Iwashita, Kazuo T. Suzuki. Identification of selenohomolanthionine in selenium-enriched Japanese pungent radish. Journal of Analytical Atomic Spectrometry 2007, 22 (11) , 1390. https://doi.org/10.1039/b707348h
- Jeffrey R. Bacon, Kathryn L. Linge, Randall R. Parrish, Luc Van Vaeck. Atomic spectrometry update. Atomic mass spectrometry. Journal of Analytical Atomic Spectrometry 2007, 22 (8) , 973. https://doi.org/10.1039/b707553g
- Anna Haug, Robin D. Graham, Olav A. Christophersen, Graham H. Lyons. How to use the world's scarce selenium resources efficiently to increase the selenium concentration in food. Microbial Ecology in Health and Disease 2007, 19 (4) , 209-228. https://doi.org/10.1080/08910600701698986