Abstract

In recent years, the chemical speciation of several species has been increasingly monitored and investigated, employing electrospray ionization mass spectrometry (ESI-MS). This soft ionization technique gently desolvates weak metal–ligand complexes, taking them in the high vacuum sectors of mass spectrometric instrumentation. It is, thus, possible to collect information on their structure, energetics, and fragmentation pathways. For this reason, this technique is frequently chosen in a synergistic approach to investigate competitive ligand exchange-adsorption otherwise analyzed by cathodic stripping voltammetry (CLE-ACSV). ESI-MS analyses require a careful experimental design as measurement may face instrumental artifacts such as ESI adduct formation, fragmentation, and sometimes reduction reactions. Furthermore, ESI source differences of ionization efficiencies among the detected species can be misleading. In this mini-review are collected and critically reported the most recent approaches adopted to mitigate or eliminate these limitations and to show the potential of this analytical technique.

Highlights

  • ESI has been developed as a soft ionization technique (Whitehouse et al, 1985) that gently takes into the gas phase metal–ligand complexes and allows gathering a wealth of information on their dissociation energetics, shapes, and fragmentation pathways

  • The authors were capable of stabilizing simple uranyl complexes during the ionization process and ion-mobility separation to aid speciation and isotope profile analysis

  • Theoretical calculations can be more compared to experimental results, and the model geometry suggests the structural information that is lacking in an electrospray ionization-mass spectrometry (ESI-MS) spectrum

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Summary

INTRODUCTION

The IUPAC has defined the term “speciation analysis” as the “analytical activities of identifying and/or measuring the quantities of one or more individual chemical species in a sample.” It is defined as “speciation of an element” the “distribution of an element amongst defined chemical species in a system.” Taking into account the development of the field and the wave of other -omic sciences, the term “metallomics” has been recently coined, defining “metallome” as the ensemble of metals and metalloids present in cells or tissues taking into consideration their nature, quantity, and localization. The IUPAC has defined the term “speciation analysis” as the “analytical activities of identifying and/or measuring the quantities of one or more individual chemical species in a sample.”. It is defined as “speciation of an element” the “distribution of an element amongst defined chemical species in a system.”. Taking into account the development of the field and the wave of other -omic sciences, the term “metallomics” has been recently coined, defining “metallome” as the ensemble of metals and metalloids present in cells or tissues taking into consideration their nature, quantity, and localization. For metallomics approaches, the combined use of chromatographic (or electrophoresis) separation and inductively coupled plasma-mass spectrometry (ICP-MS) is useful, whereas electrospray ionization-mass spectrometry (ESI-MS) allows the discrimination of species containing the same metal and to obtain structural elucidation

ELECTROSPRAY IONIZATION
COUPLING ESI WITH MASS SPECTROMETRY ANALYZERS
Speciated metal Analytical approach
DESORPTION ESI AND AMBIENT MASS SPECTROMETRY APPLICATIONS
Findings
CONCLUSIONS

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