252Cf Plasma desorption (PD), matrix-assisted laser desorption (MA-LDI) and electrospray ionization (ESI) time-of-flight (TOF) mass spectrometric techniques were invented few decades ago and have been used extensively to analyze large non-volatile bio-molecules by desorbing/ ionizing them into the gaseous phase. However, since the introduction of these techniques, the ion formation and matrix effects have been under constant debate. This monograph which is the outgrowth of my doctoral dissertation, describes ionization pathways and matrix-effects in PD-, LDI-TOF MS considering...