A study of the application of graphite MALDI to the analysis of lanthanides and deconvolution of the isobaric species observed.

Matrix-assisted laser desorption/ionisation mass spectrometry has always suffered from matrix interference at low-masses making it an unsuitable method for the analysis of low molecular weight analytes. In recent years, there has been considerable interest in the use of graphite as a matrix. In this study, we demonstrate the application of colloidal graphite for the analysis of lanthanides in the positive ion mode. Positive ion mode is of academic interest as spectra are dominated by lanthanide cations, oxides, hydroxides and carbides with the metal having been reduced to oxidation state I, II or III. The ratios of the different ions are considered in terms of redox potentials of the lanthanides and rates of reaction with oxygen. Positive ion mode is shown to be useful as a rapid technique for confirming which metal(s) are present in a sample which can have an application in environmental monitoring, for example. Demonstration of a least squares approach to deconvolution is applied for the complete separation and relative quantification of the different isobaric species observed due to the complex isotope distributions of some lanthanides.

Investigation of colloidal graphite as a matrix for matrix-assisted laser desorption/ionisation mass spectrometry of low molecular weight analytes.

The analysis of low molecular weight compounds by matrix-assisted laser desorption/ionisation mass spectrometry is problematic due to the interference and suppression of analyte ionisation by the matrices typically employed - which are themselves low molecular weight compounds. The application of colloidal graphite is demonstrated here as an easy to use matrix that can promote the ionisation of a wide range of analytes including low molecular weight organic compounds, complex natural products and inorganic complexes. Analyte ionisation with colloidal graphite is compared with traditional organic matrices along with various other sources of graphite (e.g. graphite rods and charcoal pencils). Factors such as ease of application, spectra reproducibility, spot longevity, spot-to-spot reproducibility and spot homogeneity (through single spot imaging) are explored. For some analytes, considerable matrix suppression effects are observed resulting in spectra completely devoid of matrix ions. We also report the observation of radical molecular ions [M(-●) ] in the negative ion mode, particularly with some aromatic analytes. Copyright © 2016 John Wiley & Sons, Ltd.