Abstract: "A vast part of processes of chemical interest takes place in a condensed phase. The microscopic description of condensed phases is however a challenging task. Simplified environments become necessary in order to gain insights into the intrinsic molecular properties and behavior that are responsible for interesting nanoscopic and mesoscopic phenomena. The isolation of molecular systems in the gas phase, or in cold inert molecular matrices, provides such an environment. Among the soft (non-fragmentative) molecular ion sources available nowadays, we made extensive use of matrix-assited laser-desorption-ionization (MALDI), LDI and of electrospray ionization (ESI) techniques. Isolated systems can then be characterized with a variety of modern spectroscopic and mass spectrometric techniques that probe their structures and interactions. The precise definition of the molecular framework that is achieved in this approach also provides a valuable reference to validate quantum chemistry and molecular modelling methods. We present here some of our results on the optimization of LDI employing nanoparticles as co-desorbing matrices and some important results of the collisional cooling on the LDI-induced fragmentation of polyaromatic hydrocarbons. In the second part, we present our spectroscopic characterization results of gas phase species (neutral and charged) involving cyclic ethers and cyclodextrines as benchmark examples of inclusion complexes."