Biological Selenium Species and Selenium Speciation in Biological Samples

The chapter summarizes the state-of-the-art of the analytical methodology for the speciation of selenium (Se) in biological samples relevant to human health (body fluids, cell cultures, tissues, food supplements). Selenoproteins with genetically encoded s

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Biological Selenium Species and Selenium Speciation in Biological Samples Katarzyna Bierla, Joanna Szpunar, and Ryszard Lobinski

Abstract The chapter summarizes the state-of-the-art of the analytical methodology for the speciation of selenium (Se) in biological samples relevant to human health (body fluids, cell cultures, tissues, food supplements). Selenoproteins with genetically encoded selenocysteine, Se-containing proteins with Met substituted by selenomethionine, and Se-containing metabolites are discussed. Whereas gel electrophoresis followed by radiography of 75Se is the benchmark for selenoprotein and Se-containing protein detection, the recent advances in laser ablation-ICP MS allow the scanning of the gels for stable Se isotopes, increasing the number of biological systems to be investigated and enhancing the depth of the studies. The democratization of proteomics approaches opens the way to the high throughput identification of selenoproteins, although several bottlenecks, such as loss of Sec during sample preparation, identification on the basis of the part of the proteins without Se, and insufficient sensitivity, are still demanding considerable improvements of analytical methodology. In the field of metabolomics, the combined use of multidimensional HPLC with the combined Se-specific ICP MS detection and Orbitrap MSn detection, seems to be an ultimate tool for the comprehensive quantitative and qualitative Se speciation analysis. Keywords Electrospray MS orbitrap • Food supplements • Foodstuffs • HPLC-ICP MS • Human health • Selenium speciation • Selenoproteins

35.1

Introduction: Interest in Selenium (Se) Speciation Analysis in Biology

Knowledge of speciation: the identity and the concentration of the exact chemical form(s) in which Se is present in a sample is fundamental to describe its molecular mechanisms of the biological activity of this element and to delineate the specific

K. Bierla • J. Szpunar • R. Lobinski (*) CNRS-UPPA, UMR 5254, Laboratoire de Chimie Analytique Bio-inorganique et Environnement (LCABIE-IPREM), Hélioparc, 2, Avenue Pr. Angot, 64053 Pau, France e-mail: [email protected] © Springer Science+Business Media, LLC 2016 D.L. Hatfield et al. (eds.), Selenium, DOI 10.1007/978-3-319-41283-2_35

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metabolic pathways in cells and tissues. The processes concern medical, physiological and nutritional research: the role of Se in health and disease, the metabolism and activity of Se-containing active therapeutic molecules and nanoparticles, the biotechnology of Se-enriched food and feed supplements [1–3], and Se bioavailability and metabolism in food [1, 2].

35.2

Se Species of Interest

There are numerous foods and food supplements. The most important Se species of interest are described below.

35.2.1

Selenoamino acids: Selenomethionine (SeMet) and Selenocysteine (Sec)

The SeMet concentration is an important parameter to evaluate the degree of conversion of inorganic Se into organic Se. It is produced by the replacement of sulfur with Se in the biosyn