Thanks to recent technological advances and singlephoton ionization's (SPI's) ability to detect all organics,Because the human eye does not detect IR radiation, we cannot see a warm object in the dark without an IR camera or other "transformation method". MS has the same problem: it cannot directly detect the objects of intereststhe analyte moleculessbut only their ionized counterparts. Therefore, the transformation methods that ionize the analyte molecules are of particular importance to MS. The invention of new ionization methods such as MALDI or ESI for MS detection of biomolecules has had an enormous influence on the development of MS and its applications in analytical chemistry.However, many ionization methods result in the formation not only of intact molecular ions but also of ion fragments. This is particularly true for electron impact (EI) ionization, the classical ionization method for smaller molecules ranging in mass up to ∼500 Da. EI uses electrons of 70-eV kinetic energy, near where maximal ionization efficiency occurs, 1 which makes it a "hard" ionization technique because the analytes are heavily fragmented upon ionization. The molecular peak is often barely visible in the mass spectra of labile compounds, although the fragment patterns do supply information about the presence of distinct functional groups in the investigated molecules. Furthermore, the fragment patterns of unknown substances can be used for a statistically based identification by comparison with EI-MS library data. The benefits of the latter feature made MS with EI the routine spectrometric detection method for GC. However, the frequent absence of information on the molecular weight of labile compounds is a severe disadvantage of EI, hampering the identification of unknowns. Furthermore, for complex mixtures of organic compounds, EI-MS requires a preseparation method such as GC; otherwise, the overlapping complex fragment patterns cannot be deconvoluted into mass spectra of individual compounds.These shortcomings of EI have led to a continuing demand for robust fragmentation-free or "soft" ionization methods for MS. Several soft ionization techniques have been developed, including methods based on chemical ionization (CI), field ionization (FI), and photoionization (PI). More recently, MALDI and ESI emerged and became the dominant soft ionization methods for polar