Direct mass spectrometric imaging of document handwriting with laser desorption ionization and post ultraviolet photodissociation

Handwriting represents personal education and physical or psychological states. This work describes a chemical imaging technique for document evaluation that combines laser desorption ionization with post ultraviolet photo-induced dissociation (LDI-UVPD) in mass spectrometry. Taken the advantages of chromophores in ink dyes, handwriting papers were subjected to direct laser desorption ionization without additional matrix mate-rials. It is a surface-sensitive analytical method that uses a low intensity pulsed laser at 355 nm to remove chemical components from very outermost surfaces of overlapped handwritings. Meanwhile, the transfer of photoelectrons to those compounds leads to the ionization and the formation of radical anions. The gentle evaporation and ionization property enable the dissection of chronological orders. Paper documents maintain intact without extensive damages after laser irradiation. The evolving plume resulting from the irradiation of the 355 nm laser is fired by the second ultraviolet laser at 266 nm that is in parallel to the sample surface. In contrast to collision activated dissociation in tandem MS/MS, such post ultraviolet photodissociation generates much more different fragment ions through electron-directed specific cleavages of chemical bonds. LDI-UVPD can not only provide graphic representation of chemical components but also reveal hidden dynamic features such as alterations, pressures and aging.