MALDI-TOF mass spectrometry on cellulosic surfaces of fresh and photo-aged di- and triterpenoid varnish resins.

Matrix-Assisted Laser Desorption/Ionization Time-of-Flight mass spectrometry (MALDI-TOF-MS) on cellulosic surfaces is shown to be a suitable method for examining highly oxidized terpenoids, which are otherwise too difficult to determine by other techniques. By crystallization of a 2,5-dihydroxybenzoic acid (DHB) matrix and the sample solution on cellulose-coated thin layer chromatography(TLC) plates, spectra with good signal/noise ratios are obtained and no significant interferences due to matrix ions or cluster ions were produced, at least not in the range of m/z values of interest (>300 Da). The validity of the method was tested on natural di- and triterpenoid resins used as paint varnishes by Old Masters. The samples were analyzed before and after artificial light ageing. Di- and triterpenoid compounds, being very sensitive towards photo-oxidation, were found as oxidized molecules even in the raw resins and in the unexposed varnish layers. Artificial ageing simulating window-filtered daylight resulted in a stronger oxidation of the original terpenoids and the incorporation of up to six oxygen atoms per molecule could be demonstrated. Terpenoid dimers and their oxidation products were also detected.