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.

Sample preparation methods for optimal HS-AFM analysis: Duplex stainless steel.

The contact mode high-speed atomic force microscope (AFM) operates orders of magnitude faster than conventional AFMs. It is capable of capturing multiple frames per second with nanometre-scale lateral resolution and subatomic height resolution. This advancement in imaging rate allows for microscale analysis across macroscale surfaces, making it suitable for applications across materials science. However, the quality of the surface analysis obtained by high-speed AFM is highly dependent upon the standard of sample preparation and the resultant final surface finish. In this study, different surface preparation techniques that are commonly implemented within metallurgical studies are compared for samples of SAF 2205 duplex stainless steel. It was found that, while acid etching and electrolytic etching were optimal for the low resolution of optical microscopy, these methods were less suited for analysis by high resolution high-speed AFM. Mechanical and colloidal silica polishing was found to be the optimal method explored, as it provided a gentle etch of the surface allowing for high quality topographic maps of the sample surface.

Flavone as a novel matrix for the matrix-assisted laser desorption/ionisation analysis of lanthanide and transition metal salts.

The mass spectral analysis of metal salts, especially lanthanide and transition metal salts, can be challenging. Although getting information on the metal present is usually straightforward, obtaining information on the correct oxidation state and anion composition is challenging. Many ionisation techniques have some redox component to the ionisation process, which commonly results in changing the oxidation state of the metal and the associated loss of ligand and anion information. We present here a simple method for negative ion matrix-assisted laser desorption/ionisation mass spectrometry using the non-acidic flavonoid flavone as a novel matrix. This results in reliable information on the oxidation state of the metal as spectra are dominated by anion adduct ions with very little (typically no) redox processes occurring.

Methodologies for the airbrush application of MALDI matrices.

There is still a need to develop reliable and robust matrix deposition methods for matrix-assisted laser desorption/ionisation mass spectrometry that are applicable to a range of matrices, solvents and analyte types. This paper presents a robust methodology for the airbrush application of matrices along with the implications of varying the set-up and airbrush parameters. A small number of organic analytes and metal salts are analysed in both positive and negative ion modes to exemplify this methodology. In the analyses with the airbrush deposited matrices, performance was enhanced when compared to standard pipette deposition with the need for a search for sweat spots greatly diminished due to the increase homogeneity of the matrix surface and resultant analyte spots. As expected, the graphite matrices were shown to specifically outperform the organic matrices in negative ion mode.

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.