The recent developments in analytical techniques capable of providing information on the identity and quantity of heteroatom-containing biomolecules are critically discussed. Particular attention is paid to the emerging areas of bioinorganic analysis including: (i) a comprehensive analysis of the entirety of metal and metalloid species within a cell or tissue type (metallomics), (ii) the study of the part of the metallome involving the protein ligands (metalloproteomics), and (iii) the use of a heteroelement, naturally present in a protein or introduced in a tag added by means of derivatisation, for the spotting and quantification of proteins (heteroatom-tagged proteomics). Inductively coupled plasma mass spectrometry (ICP MS), used as detector in chromatography and electrophoresis, and supported by electrospray and MALDI MS, appears as the linchpin analytical technique for these emerging areas. This review focuses on the recent advances in ICP MS in biological speciation analysis including sensitive detection of non-metals, especially of sulfur and phosphorus, couplings to capillary and nanoflow HPLC and capillary electrophoresis, laser ablation ICP MS detection of proteins in gel electrophoresis, and isotope dilution quantification of biomolecules. The paper can be considered as a followup of a previous review by the author on a similar topic (: J. Szpunar, Analyst, 2000, 125, 963).

The emerging field of metallomics refers to the entirety of research activities aimed at the understanding of the molecular mechanisms of metal-dependent life processes. This critical review discusses the concept of metallomics with a focus on analytical techniques and methods for the probing of interactions between metal ions and the organism’s genome and the derived -omes: proteome and metabolome. Particular attention is paid to the in vivo screening for the native metal–protein and metal–metabolite complexes by hyphenated techniques that combine a high-resolution separation technique (gel electrophoresis, chromatography or capillary electrophoresis) with sensitive elemental (inductively coupled plasma, ICP) or molecular (electrospray or MALDI) mass spectrometric detection. The contribution of bioinformatics to the prediction of metal-binding sequences in proteins and the role of molecular biology approaches for the detection of metal-dependent genes, proteins and metabolites are highlighted (115 references).

The state-of-the-art of species-selective analysis for trace metals and metalloids in biological materials by chromatographic and electrophoretic separation techniques with element selective detection is critically reviewed. The species of interest include organoarsenic, organoselenium and metal complexes with bioligands such as phytochelatins, metallothioneins, proteins and polysaccharides. The separation mechanisms discussed include size-exclusion, anion- and cation-exchange and reversed-phase HPLC and flatbed and capillary zone electrophoresis. Advantages and limitations of various element selective (e.g., AAS, ICP-AES and ICP-MS) and molecule specific (electrospray MS/MS) detection techniques used on- and off-line are discussed. The applications of coupled techniques to the analysis of biological materials are comprehensively reviewed in tabular form. Attention is paid to the sample preparation and sources of error in bioinorganic speciation analysis.