Dual-polarity MALDI mass spectrometry and imaging of oil binders and fatty acids in artworks using cyanographene as a single matrix

Abstract

Matrix-assisted laser desorption ionization mass spectrometry (MALDI MS) and imaging mass spectrometry (IMS) are being increasingly recognized for the detection and visualization of various organic species including lipids and fatty acids. Nevertheless, most MALDI matrices perform optimally in one ionization mode. This study investigates the performance of cyano derivative of graphene (G-CN) as a matrix in two polarities of MALDI MS and IMS for the detection of oil binders and fatty acids in artworks, and compares it with classical MALDI matrices (2,5-dihydroxybenzoic acid, 9-aminoacridine). Results revealed the ability of G-CN to provide high quality positive and negative mass spectra of oils and fatty acids, respectively, with lowest matrix-induced interferences among tested matrices and minimal effects of the presence of inorganic pigments. The newly developed approach makes both oil and fatty acid identifiable in a single spot simply by covering the sample surface with one matrix and switching the polarity in MALDI without any sample manipulation. G-CN offers effective matrix to analyte energy transfer, ability to detect components in less than 100 ng of oil at a MALDI spot and lesser analyte fragmentation than the compared conventional matrices. Furthermore, it enables direct mapping of specific m/z features corresponding to triacylglycerol (TAG), products of TAG oxidation and deprotonated acids using one nanoparticle matrix in MALDI IMS. This research shows potential for technical innovations in the study of art micro-environments and degradation phenomena of historical artworks.

Keywords: Artwork analysis; Fatty acids; Graphene derivative; MALDI imaging mass spectrometry; Nanomaterials; Oil binders.