Abstract

The evolution of the field of element speciation, from the targeted analysis for specific element species toward a global exploratory analysis for the entirety of metal- or metalloid-related compounds present in a biological system (metallomics), requires instrumental techniques with increasing selectivity and sensitivity. The selectivity of hyphenated techniques, combining chromatography, and capillary electrophoresis with element-specific detection (usually inductively coupled plasma mass spectrometry, ICP MS), is often insufficient to discriminate all the species of a given element in a sample. The necessary degree of specificity can be attained by ultrahigh-resolution (R >100,000 in the m/z < 1,000 range for a 1 s scan) mass spectrometry based on the Fourier transformation of an image current of the ions moving in an Orbitrap or an ion cyclotron resonance (ICR) cell. The latest developments, allowing the separate detection of two ions differing by a mass of one electron (0.5 mDa) and the measurement of their masses with a sub-ppm accuracy, make it possible to produce comprehensive lists of the element species present in a biological sample. Moreover, the increasing capacities of multistage fragmentation often allow their de novo identification. This perspective paper critically discusses the potential state-of-the-art of implementation, and challenges in front of FT (Orbitrap and ICR) MS for a large-scale speciation analysis using, as example, the case of the metabolism of selenium by yeast.

Highlights

  • Hyphenated techniques combining the selectivity of chromatography or capillary electrophoresis with an atomic absorption (AAS), fluorescence (AFS), microwave plasma source emission (MIP AES), or inductively coupled plasma mass spectrometry (ICP MS) detectors remained a standard tool for speciation analysis (Lobinski, 1997; Szpunar et al, 2003)

  • The increasing detection sensitivity has put in evidence the fact that, in many cases, chromatography, even multidimensional, was unable to ensure the molecular specificity of the analytical signal measured

  • When all the complexes of an element with proteins and low-molecularweight biological ligands have to be determined within one run, the chromatographic peak capacity becomes insufficient to offer the baseline separation of all its compounds of interest; in addition, risks, inherent to chromatography, of incomplete recoveries, and species transformation occur (Lobinski et al, 2010)

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Summary

INTRODUCTION

Hyphenated techniques combining the selectivity of chromatography or capillary electrophoresis with an atomic absorption (AAS), fluorescence (AFS), microwave plasma source emission (MIP AES), or inductively coupled plasma mass spectrometry (ICP MS) detectors remained a standard tool for speciation analysis (Lobinski, 1997; Szpunar et al, 2003). Their success was based on the detector’s selectivity for the target element and on the baseline separation of the target species from other species of the same element

FT Mass Spectrometry for Selenometabollomics
Sample introduction Nr of species
RP HPLC
FT ICR MS Detection of Se Species
Orbitrap MSn Species Identification
Selenium Isotopic Pattern Recognition
Findings
Lessons From the Chemistry
Full Text
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