Method development for the analysis of resinous materials with MALDI-FT-ICR-MS: novel internal standards and a new matrix material for negative ion mode

Matrix-assisted laser desorption/ionization (MALDI) is a mass spectrometry (MS) ionization technique suitable for a wide variety of sample types including highly complex ones such as natural resinous materials. Coupled with Fourier transform ion cyclotron resonance (FT-ICR) mass analyser, which provides mass spectra with high resolution and accuracy, the method gives a wealth of information about the composition of the sample. One of the key aspects in MALDI-MS is the right choice of matrix compound. We have previously demonstrated that 2,5-dihydroxybenzoic acid is suitable for the positive ion mode analysis of resinous samples. However, 2,5-dihydroxybenzoic acid was found to be unsuitable for the analysis of these samples in the negative ion mode. The second problem addressed was the limited choice of calibration standards offering a flexible selection of m/z values under m/z 1000. This study presents a modified MALDI-FT-ICR-MS method for the analysis of resinous materials, which incorporates a novel matrix compound, 2-aminoacridine for the negative ion mode analysis and extends the selection of internal standards with m/z <1000 for both positive (15 different phosphazenium cations) and negative (anions of four fluorine-rich sulpho-compounds) ion mode. The novel internal calibration compounds and matrix material were tested for the analysis of various natural resins and real-life varnish samples taken from cultural heritage objects. Copyright (c) 2017 John Wiley & Sons, Ltd.