Abstract
Selenium is an essential element incorporated to different proteins with important biological functions in connection to antioxidant activity, cancer-protective properties, neurodegenerative pathologies, and prevention of effects of diabetes, among others. In addition, selenoamino acids play a basic role in the global equilibrium of key selenium-biomolecules synthesis, including selenoprotein P, selenoalbumin, and glutathione peroxidase. Homeostasis of these selenium-containing biomolecules involves different organs in living organisms including human, and bloodstream is the connection fluid in this process. Therefore, it is very important to have an analytical methodology suitable for selenium proteins and metabolites speciation in serum and plasma samples. For this purpose, a simultaneous speciation method for Se-containing biomolecules in serum/plasma is described on the basis of in series three-dimensional chromatography: size exclusion, affinity, and anion exchange high performance liquid chromatography (3D/SE-AF-AEC-HPLC), using different columns of each type and hyphenation to inductively coupled plasma-(quadrupole) mass spectrometry (ICP-MS). The method allows the quantitative simultaneous analysis of selenoprotein P (SeP), extracellular glutathione peroxidase (eGPx), selenoalbumin (SeAlb), selenite, and selenate in serum (from human and mouse) using species-unspecific isotope dilution (SUID). In addition, a simplified two-dimensional approach (2D/SE-AF-HPLC-SUID-ICP-MS) is described when selenium metabolites are globally analyzed. The method provides detection limits in the range 0.2–1.3 ng of Se g−1 and avoids typical interferences in this matrix from chloride and bromide with a chromatographic runtime less than 35 min.
Access this chapter
Tax calculation will be finalised at checkout
Purchases are for personal use only
References
Ursini F, Heim S, Kiess M, Maiorino M, Roveri A, Wissing J, Flohé L (1999) Dual function of the selenoprotein PHGPx during sperm maturation. Science 285:1393–1396. doi:10.1126/science.285.5432.1393
Yoneda S, Suzuki KT (1997) Equimolar Hg-Se complex binds to selenoprotein P. Biochem Biophys Res Commun 231:7–11. doi:10.1006/bbrc.1996.6036
Mostert V (2000) Selenoprotein P: properties, functions, and regulation. Arch Biochem Biophys 376:433–438. doi:10.1006/abbi.2000.1735
Thomson CD (1998) Selenium speciation in human body fluids. Analyst 123:827–831. doi:10.1039/a707292i
Rayman MP, Infante HG, Sargent M (2008) Food-chain selenium and human health: spotlight on speciation. Br J Nutr 100:238–253. doi:10.1017/S0007114508922522
Roman M, Jitaru P, Agostini M, Cozzi G, Pucciarelli S, Nitti D, Bedin C, Barbante C (2012) Serum seleno-proteins status for colorectal cancer screening explored by data mining techniques – a multidisciplinary pilot study. Microchem J 105:124–132. doi:10.1016/j.microc.2012.02.004
Jitaru P, Goenaga-Infante H, Vaslin-Reimann S, Fisicaro P (2010) A systematic approach to the accurate quantification of selenium in serum selenoalbumin by HPLC-ICP-MS. Anal Chim Acta 657:100–107. doi:10.1016/j.aca.2009.10.037
Suzuki KT, Ogra Y (2002) Metabolic pathway for selenium in the body: speciation by HPLC-ICP MS with enriched Se. Food Addit Contam 19:974–983. doi:10.1080/02652030210153578
García-Sevillano MA, García-Barrera T, Navarro F, Gómez-Ariza JL (2014) Absolute quantification of superoxide dismutase in cytosol and mitochondria of mice hepatic cells exposed to mercury by a novel metallomic approach. Anal Chim Acta 842:42–50. doi:10.1016/j.aca.2014.07.014
Lunøe K, Martínez-Sierra JG, Gammelgaard B, Alonso JIG (2012) Internal correction of spectral interferences and mass bias for selenium metabolism studies using enriched stable isotopes in combination with multiple linear regression. Anal Bioanal Chem 402:2749–2763. doi:10.1007/s00216-012-5747-7
Humann-Ziehank E, Ganter M, Michalke B (2016) Selenium speciation in paired serum and cerebrospinal fluid samples of sheep. J Trace Elem Med Biol 33:14–20. doi:10.1016/j.jtemb.2015.07.010
Roman M, Lapolla A, Jitaru P, Sechi A, Cosma C, Cozzi G, Cescon P, Barbante C (2010) Plasma selenoproteins concentrations in type 2 diabetes mellitus – a pilot study. Transl Res 156:242–250. doi:10.1016/j.trsl.2010.07.006
Hinojosa Reyes L, Marchante-Gayón JM, García Alonso JI, Sanz-Medel A (2003) Quantitative speciation of selenium in human serum by affinity chromatography coupled to post-column isotope dilution analysis ICP-MS. J Anal At Spectrom 18:1210–1216. doi:10.1039/b305455a
Jitaru P, Cozzi G, Gambaro A, Cescon P, Barbante C (2008) Simultaneous speciation analysis of glutathione peroxidase, selenoprotein P and selenoalbumin in human serum by tandem anion exchange-affinity HPLC and on-line isotope dilution ICP-quadrupole MS. Anal Bioanal Chem 391:661–669. doi:10.1007/s00216-008-2043-7
Sariego Muñiz C, Marchante-Gayón JM, García Alonso JI, Sanz-Medel A (1999) Multi-elemental trace analysis of human serum by double-focusing ICP-MS. J Anal At Spectrom 14:193–198
García-Barrera T, Gómez-Ariza JL, González-Fernández M, Moreno F, García-Sevillano MA, Gómez-Jacinto V (2012) Biological responses related to agonistic, antagonistic and synergistic interactions of chemical species. Anal Bioanal Chem 403:2237–2253. doi:10.1007/s00216-012-5776-2
Rodríguez-González P, Marchante-Gayón JM, García Alonso JI, Sanz-Medel A (2005) Isotope dilution analysis for elemental speciation: a tutorial review. Spectrochim Acta Part B 60:151–207. doi:10.1016/j.sab.2005.01.005
Palacios Ò, Ruiz Encinar J, Schaumlöffel D, Lobinski R (2006) Fractionation of selenium-containing proteins in serum by multiaffinity liquid chromatography before size-exclusion chromatography-ICPMS. Anal Bioanal Chem 384:1276–1283. doi:10.1007/s00216-005-0286-0
Xu M, Yang L, Wang Q (2008) Quantification of selenium-tagged proteins in human plasma using species-unspecific isotope dilution ICP-DRC-qMS coupled on-line with anion exchange chromatography. J Anal At Spectrom 23:1545–1549. doi:10.1039/b804935a
Koyama H, Omura K, Ejima A, Kasanuma Y, Watanabe C, Satoh H (1999) Separation of selenium-containing proteins in human and mouse plasma using tandem high-performance liquid chromatography columns coupled with inductively coupled plasma-mass spectrometry. Anal Biochem 267:84–91. doi:10.1006/abio.1998.2949
Jitaru P, Prete M, Cozzi G, Turetta C, Cairns W, Seraglia R, Traldi P, Cescon P, Barbante C (2008) Speciation analysis of selenoproteins in human serum by solid-phase extraction and affinity HPLC hyphenated to ICP-quadrupole MS. J Anal At Spectrom 23:402–406. doi:10.1039/B712693J
Jitaru P, Cozzi G, Seraglia R, Traldi P, Cescon P, Barbante C (2010) Towards an improved qualitative and quantitative determination of glutathione peroxidase, selenoprotein P and selenoalbumin in human serum by HPLC coupled to ICP-MS. Anal Methods 2:1382–1387. doi:10.1039/c0ay00173b
García-Sevillano MA, García-Barrera T, Gómez-Ariza JL (2014) Simultaneous speciation of selenoproteins and selenometabolites in plasma and serum by dual size exclusion-affinity chromatography with online isotope dilution inductively coupled plasma mass spectrometry. Anal Bioanal Chem 406:2719–2725. doi:10.1007/s00216-014-7629-7
Deagen JT, Butler JA, Zachara BA, Whanger PD (1993) Determination of the distribution of selenium between glutathione peroxidase, selenoprotein P, and albumin in plasma. Anal Biochem 208:176–181. doi:10.1006/abio.1993.1025
Harrison I, Littlejohn D, Fell GS (1996) Distribution of selenium in human blood plasma and serum. Analyst 121:189–194. doi:10.1039/an9962100189
Sariego Muñiz C, Marchante Gayón JM, García Alonso JI, Sanz-Medel A (2001) Speciation of essential elements in human serum using anion-exchange chromatography coupled to post-column isotope dilution analysis with double focusing ICP-MS. J Anal At Spectrom 16:587–592. doi:10.1039/b100947h
Vanhaecke F, De Wannemacker G, Moens L, Dams R, Latkoczy C, Prohaska T, Stingeder G (1998) Dependence of detector dead time on analyte mass number in inductively coupled plasma mass spectrometry. J Anal At Spectrom 13:567–571
Encinar JR, Schaumlöffel D, Ogra Y, Lobinski R (2004) Determination of Selenomethionine and Selenocysteine in Human Serum Using Speciated Coupled Plasma Collision Cell Mass Spectrometry. Anal Chem 76:6635–6642
García-Sevillano MA, García-Barrera T, Gómez-Ariza JL (2013) Development of a new column switching method for simultaneous speciation of selenometabolites and selenoproteins in human serum. J Chromatogr A 1318:171–179. doi:10.1016/j.chroma.2013.10.012
Jitaru P, Roman M, Barbante C, Vaslin-Reimann S, Fisicaro P (2010) Challenges in the accurate speciation analysis of selenium in humans: first report on indicative levels of selenoproteins in a serum certified reference material for total selenium (BCR-637). Accredit Qual Assur 15:343–350
García-Sevillano MA, Rodríguez-Moro G, García-Barrera T, Navarro F, Gómez-Ariza JL (2015) Biological interactions between mercury and selenium in distribution and detoxification processes in mice under controlled exposure. Effects on selenoprotein. Chem Biol Interact 229:82–90. doi:10.1016/j.cbi.2015.02.001
Chen C, Yu H, Zhao J, Li B, Qu L, Liu S, Zhang P, Chai Z (2006) The roles of serum selenium and selenoproteins on mercury toxicity in environmental and occupational exposure. Environ Health Perspect 114:297–301. doi:10.1289/ehp.7861
Shiobara Y, Suzuki KT (1998) Binding of selenium (administered as selenite) to albumin after efflux from red blood cells. J Chromatogr B Biomed Sci Appl 710:49–56
Santos C, García-Fuentes E, Callejón-Leblic B, García-Barrera T, Gómez-Ariza JL, Rayman MP, Velasco I (2017) Selenium, selenoproteins and selenometabolites in mothers and babies at the time of birth. Br J Nutr 117:1304–1311. doi:10.1017/S0007114517001155
Gonzalez-Fernández M, García-Sevillano MA, Jara-Biedma R, García-Barrera T, Vioque A, López-Barea J, Pueyo C, Gómez-Ariza JL (2011) Size characterization of metal species in liver and brain from free-living (Mus spretus) and laboratory (Mus Musculus) mice by SEC-ICP-MS: application to environmental contamination assessment. J Anal At Spectrom 26:141–149. doi:10.1039/C0JA00127A
Acknowledgments
The authors thanks to Spanish Ministry of Economy and Competitiveness (Grant CTM2015-67902-C2-1-P and Regional Ministry of Economy, Innovation, Science and Employment (Andalusian Government, Spain), Grant P12-FQM-0442. Gema Rodríguez-Moro thanks Spanish Ministry of Economy and Competitiveness for a predoctoral scholarship BES-2013-064501, and Belén Callejón-Leblic thanks the Ministerio de Educación for a predoctoral scholarship FPU13/03615. Finally, the authors are grateful to FEDER (European Community) for financial support, grants number UNHU13-1E-1611 and UNHU15-CE-3140.
Author information
Authors and Affiliations
Corresponding author
Editor information
Editors and Affiliations
Rights and permissions
Copyright information
© 2018 Springer Science+Business Media LLC
About this protocol
Cite this protocol
Callejón-Leblic, B., Rodríguez-Moro, G., García-Barrera, T., Gómez-Ariza, J.L. (2018). Simultaneous Speciation of Selenoproteins and Selenometabolites in Plasma and Serum. In: Chavatte, L. (eds) Selenoproteins. Methods in Molecular Biology, vol 1661. Humana Press, New York, NY. https://doi.org/10.1007/978-1-4939-7258-6_12
Download citation
DOI: https://doi.org/10.1007/978-1-4939-7258-6_12
Published:
Publisher Name: Humana Press, New York, NY
Print ISBN: 978-1-4939-7257-9
Online ISBN: 978-1-4939-7258-6
eBook Packages: Springer Protocols